In recent years, novelty has been proposed as a potential fourth basic psychological need. In the present study, the behavior of novelty resulting from support from the Physical Education teacher was evaluated in 723 students with an average age of 13.30 years old. The first objective was to validate the Support for Basic Psychological Needs-4 (SBPN-4) in Physical Education questionnaire, which included support for the novelty factor. The second objective was to test the mediation model in order to confirm the effect of support for novelty in relation to basic psychological needs and intrinsic motivation. The results obtained show that the Support for Basic Psychological Needs-4 (SBPN-4) questionnaire is a valid and reliable tool. On the other hand, support for novelty predicts satisfaction of basic psychological needs, particularly novelty satisfaction, which in turn predicts intrinsic motivation. These results show how the students are capable of perceiving the teacher’s support for novelty and how this positively influences their intrinsic motivation. Further investigations are required to continue developing our knowledge of the role of novelty as a basic psychological need. Improvement of the educational system and, moreover, the development of students happens when we increase the motivation of those involved . One of Amongst the social factors presented within the educational field, the role of the teacher has been shown as the most determinant . In thisParticularly in Physical Education, the importance of SDT has been widely studied and has yielded numerous benefits ,13,14,15Given the importance of evaluating social factors related to the teacher from multiple perspectives, the Questionnaire on Support of the Basic Psychological Needs in Physical Education (CANPB)  was desiRecent studies  have proDeparting from the theoretical framework developed in the aforementioned studies on the role of novelty ,21,22,23The present investigation attempts to gain further knowledge on how novelty may function as a fourth basic psychological need. Particularly, following recommendations from previous studies ,21,26, nOverall, the principal objective of the study was to provide evidence for the possible inclusion of novelty as the fourth basic psychological need. With this aim in mind, two further principal objectives were formulated, the first being to adapt the Support for Basic Psychological Needs-4 (BPNS4) in Physical Education questionnaire to include the novelty factor. The second objective consisted of testing a mediation model that included support for novelty, the other BPNs and intrinsic motivation in PE. Thus, the following hypotheses were presented: 1) the BPNS4 will present adequate psychometric properties; (2) support for novelty will predict the satisfaction of BPNs (including the satisfaction of novelty), which, in turn, will predict intrinsic motivation. It is hoped that the findings obtained in this study continue to help clarify the role played by novelty as the fourth BPN contributing to the third, fourth, and fifth criteria established by Deci and Ryan [ the BPNSParticipants were 723 (349 boys and 374 girls) secondary school students aged between 11 and 16 years . Children were recruited from one subsidized and three public secondary schools in the province of Huelva (Spain). Students from the four age groups of lower secondary education were included: 212 from Year 7, 226 Year 8, 224 from Year 9, and 61 from Year 10 . The SBPN4 was composed of the 12 items of the Support for Basic Psychological Needs in Physical Education questionnaire  augmenteThe stem statement “In my Physical Education class, the teacher…” preceded the items of the SBPN4. The SBPN4 is comprised of four subscales: SBPN4-Autonomy , SBPN4-Competence , SBPN4-Relatedness , and SBPN4-Novelty . Participants were asked to rate each item on a five-point Likert-type scale, ranging from 1 “strongly disagree” to 5 “strongly agree”.The BPNS4 is made up of the 12 items of the Basic Psychological Needs in Exercise Scale ,30 and tThe intrinsic motivation subscale of a revised version of the Perceived Locus of Causality Scale ,32 was uThe current study was conducted in accordance with the ethical principles of the American Psychological Association . The stuParticipation in the study was solicited through direct contact with school administrators and school boards. Four schools agreed to participate. As requested by the Ethics Committee, all participants provided written consent and their parents or legal guardians also gave consent for their children to participate in the study. Before administering the questionnaire to the entire sample, a pilot sample of 50 students completed the questionnaire. Our request for comments on the clarity of the questionnaire resulted in positive comments that supported the intelligibility of the items. The questionnaire was administered in the classroom setting. In order to ensure the anonymity and confidentiality of the responses, no identifying information was used. A member of the research team was present during the administration of the questionnaire. Completion of the questionnaire was straightforward and took approximately 20 min.p < 0.01 significance level was adopted when comparing competing models.Confirmatory factor analysis (CFA) was used to provide validity evidence of the four-factor structure of the SBPN4. The fit of the hypothesized four-factor model was tested against two competing models: a one-factor model and a second-order factor model. As there was indication of multivariate non-normality in the data (standardized Mardia’s kurtosis statistics was 37.22), a robust maximum likelihood estimation method was used . AccordiMulti-group CFA was used to test the measurement invariance of the SBPN4 across gender. The level of measurement invariance was determined by imposing increasingly restrictive constraints to the baseline unconstrained multi-group model and comparing the fit of successive models. Following Meredith , configuA multiple mediation model was used to test if the effects of teacher support for novelty on intrinsic motivation was mediated by the satisfaction of basic psychological needs. Bootstrapped estimates of the direct and indirect effects of novelty support were computed using path analysis.Lavaan 0.6–5  and SemtThe hypothesized factor structure of the SBPN4 is a four-factor simple structure in which each item only loads on its respective factor, allowing correlations between factors but not correlations between items’ residual error terms. A CFA model was fit to the data to test this hypothesized factor structure of the SBPN4. The results of the analysis show a good fit of the four-factor model . The estimates of the factor loadings and factor covariances are presented in the p < 0.001) and the one-factor model . Given that the factors were highly correlated, possibly indicating the existence of a common factor, two competing models were also tested: a one-factor model in which all the items were forced to load on a single factor and a second-order factor model with a general factor accounting for the correlations among first-order factors. Summary fit indices from the CFAs of these models are displayed in p > 0.01 for all tests) and the small changes in CFI and RMSEA suggested that metric, scalar, and uniqueness invariance are also tenable (see p = 0.904), which provides good support for the invariance of latent means across gender.Measurement invariance of the SBPN4 across gender was evaluated using multi-group CFA. The measurement invariance of the four-factor model across boys and girls was examined by testing four increasingly restrictive models: (1) a model in which the same four-factor structure was estimated simultaneously in both gender groups ; (2) a model that extends the configural model by imposing equality constraints on factor loadings across gender (metric invariance model); (3) a model with factor loadings and item intercepts constrained to be equal across boys and girls ; and (4) a model with factor loadings, item intercepts and residual variances constrained to equality across gender (uniqueness invariance model). Summary fit statistics are presented in able see . Given tThe internal consistency estimates , means, standard deviations, and correlations of SBPN4, BPNS4, and intrinsic motivation scores are presented in p < 0.001, revealed that scores on SBPN4-Novelty were significantly higher than SBPN4-Autonomy  and significantly lower than SBPN4-Competence  and SBPN4-Relatedness . The same pattern of results was observed for BPNS4 scores.Repeated measurements ANOVA of the SBPN4 scores, F  = 510.07, The Pearson correlation coefficients between SBPN4-Novelty and the other study variables ranged from 0.25 to 0.76. This was strongly correlated with the other SBPN4 subscales, weakly to strongly correlated with the BPNS4 subscales and strongly correlated with intrinsic motivation (60). Moreover, intrinsic motivation was moderately to highly correlated with all the SBPN4 and BPNS4 subscales, with correlations ranging from 0.40 for BPNS4-Satisfaction to 0.66 for BPNS4-Novelty.A multiple mediation analysis was performed to test if the effects of teacher support for novelty on intrinsic motivation was mediated by the satisfaction of the basic psychological needs of autonomy, competence, relatedness, and novelty. Standardized estimates of the bootstrapped path analysis are presented in p < 0.01). The multiple mediation model explained 57.6% of the variance in intrinsic motivation. On the other hand, novelty support explained 44.7%, 32.4%, 12.2%, and 6.5% of the variances of novelty satisfaction, autonomy satisfaction, competence satisfaction, and relatedness satisfaction, respectively.Bootstrap tests showed that all the paths, except for the path from relatedness satisfaction to intrinsic motivation, were statistically significant . An examination of specific indirect effects indicated that novelty satisfaction , autonomy satisfaction  and competence satisfaction  were significant mediators of the relationship between novelty satisfaction and intrinsic motivation.The effect of novelty support on intrinsic motivation was only partially mediated by the satisfaction of psychological needs , trendy physical-expressive activities , or activities outside of the school environment . Another strategy with the aim of developing novelty could be the use of digital resources, such as mobile applications , the use of activities that until now have been employed very little in PE classes , the use of different materials or of other innovative materials . In short, transformation of the teaching-learning process in order to create new possibilities and to cultivate curiosity will depend on the awareness, involvement, and creativity of teachers .Despite the results obtained, it is necessary to take into account a number of considerations and to be cautious with regards to the inclusion of novelty as a fourth BPN. The present investigation has a number of limitations, such as the common method bias . The meaThe objective of the study was to test the behavior of the need for novelty as a possible fourth BPN in the self-determination theory , particu


Because this method used supercritical CO2 as the solvent to dissolve the coating material, we avoided environmental pollution from organic solvents, saved the energy required to evaporate/remove organic solvents, realized a uniform coating film on the fine particles, and prevented agglomeration of the coating particles. The solubilities of the five silicone resins used as coating materials were measured using the flow method, and the data were well correlated by Chrastil’s equation with an average deviation of 5.7%. Resins comprising numerous methyl-group side chains exhibited high solubilities and were suitable coating materials. A new semi-flow-type coating method using supercritical CO2 was also developed, which deposited a film with a uniform thickness of 0.2–1.3 μm on whole fine particles. Notably, in this method, the film thickness was easily controlled. A simple and rapid technique was developed for measuring the coating thickness using X-ray fluorescence analysis. The model for calculating the coating film thickness was based on the material balance of the coating material. This model satisfactorily predicted the thickness with an average error of 0.085 μm by measuring the solubility of the coating material in supercritical CO2, integrated flow volume of supercritical CO2, particle diameter, density and charged weight of the fine particle, and coating material density.An environmentally friendly and efficient polymer coating method for micro-sized particles was developed using supercritical CO Polymer coating is important for surface functionalization and fabricating composite coatings of micro- and nano-sized particles. This technology is used in many fields, such as medicine, food, cosmetics, smart materials, and electronics; the most notable application is in drug delivery ,2, in wh2 has been studied in several fields because it is an environmentally friendly solvent that acts as a promising alternative to toxic and flammable organic solvents. Moreover, it has moderate critical constants , large solvating power for organic materials, low viscosity, high diffusivity, and near-zero surface tension [2 can dissolve the coating material easily and rapidly, and deliver it to the immediate vicinity of particle surfaces. Thus, the use of supercritical CO2 enables the production of polymeric materials with fillers, in which micro- or nano-sized fillers are dispersed in the polymer [Supercritical CO tension . These p polymer . Further polymer .Polymer coating technologies have long employed wet coating methods. These methods use numerous solvents to dissolve coating polymers or monomers. Moreover, coating materials are usually hydrophobic and require organic solvents, which can pollute the environment and require significant energy for their evaporation and removal from the coating materials. The most commonly used wet coating method is the spray drying method , wherein2. Therefore, the utilization of silicone resin coating using supercritical CO2 could help overcome the aforementioned problems.Silicone resins are non-toxic and possess excellent insulating, heat, and weather-resistant properties. Such resins are used in cosmetics and electrical wiring as coating and insulating materials, respectively. The spray drying method is often used industrially for silicone resin coating; however, problems, such as the agglomeration and non-uniformity of the film thickness of the coated materials, exist. Silicone resins are readily soluble in supercritical CO2. Typical applications of this method include encapsulation of drugs, bioactive materials, and cosmetic ingredients [2 is necessary.For over 20 years, much attention has been paid to polymer coating technology using supercritical COredients ,13,14,152, the viscosity of the melting polymer is significantly decreased by the supercritical CO2, and the fillers disperse in the polymer effectively. This reduction in polymer viscosity and glass transition temperature in supercritical CO2 is an important phenomenon for polymer processing, including in our research.Another application is the synthesis of polymer-inorganic filler nanocomposites. In recent times, excellent properties and promising applications of these materials have been reported ,17,18,192 to produce a uniform coating film on micro-sized particles and to control and predict the film thickness. For this purpose, the following factors were examined: (1) Measuring the solubility of the coating polymer in supercritical CO2, in which the solubilities of five types of silicone resins were measured by the flow method and correlated using Chrastil’s equation. (2) The development of a semi-flow-type coating method, in which the applicability of a new coating method was examined to quickly and uniformly produce polymer coatings. (3) The development of a simple and quick method for measuring the thickness of the coating film; the usefulness of an X-ray fluorescence-based analysis was verified. (4) Establishing a model for calculating the thickness of the coating film. The model was based on the material balance of the coating polymer, and its applicability was investigated using the experimental data.The purpose of this study was the establishment of a coating technology using supercritical CO2. The particles were spherical and possessed irregularities, with an average particle size of 35 μm and a true density of 4.89 g/cm3. Micro-sized ferrite particles were used as the core material for coating in supercritical CO2 were measured. Such resins comprise siloxane bonds in the main chain and alkyl or phenyl groups in the side chain. The physical properties and structures of the five silicone resins used in this study are presented in Silicone resins were used as coating materials for the ferrite fine particles, and their solubilities in supercritical COCarbon dioxide  was used as the solvent for the coating agent, while chloroform  was used for trapping the silicone resin, analysis, and equipment cleaning. Acetone  was used for equipment washing.2 discharged from the cylinder (1) was cooled to 5 °C by the cooler (2), liquefied, and then introduced into the saturator (4) by the high-pressure pump (3). The saturator was an SUS316 cylindrical vessel with an inner diameter of 50 mm, depth of 65 mm, and inner volume of 125 cm3, and the maximum working pressure was 30 MPa. The coating material was placed in the saturator, which was immersed in a constant-temperature water bath (5) to control its temperature to an accuracy of ±0.1 °C. A stirrer (6) was installed to agitate the interior of the saturator. The CO2 in the saturator was heated above the critical temperature to achieve a supercritical state. The pressure was controlled to an accuracy of ±0.1 MPa by an automatic back pressure regulator (8) installed downstream of the saturator. The supercritical CO2 in the saturator dissolved the coating material to saturation solubility. The time required to reach dissolution equilibrium was reduced by stirring the interior of the saturator. After leaving the saturator, the supercritical CO2 containing the coating material was depressurized to atmospheric pressure by the automatic back pressure regulator, and the coating material was deposited and recovered in chloroform in the trap bottles (9). The weight of the coating material in chloroform was determined by Ultraviolet-visible spectrophotometry or High-Performance Liquid Chromatography, while the integrated flow volume of the CO2 at atmospheric pressure was measured by a gas meter (10). The piping from the constant-temperature water bath to the automatic back pressure regulator and the automatic back pressure regulator were maintained at approximately the same temperature as that of the constant-temperature water bath using a ribbon heater (7), so as not to precipitate the coating material from the supercritical CO2.2 from the CO2 cylinder was introduced into the saturator. The saturator temperature and pressure were increased to the aforementioned values using the constant-temperature water bath and high-pressure pump. Subsequently, the saturator was closed by closing valves 2 and 3, after which it was stirred for 2–3 h so that the supercritical CO2 and silicone resin were in dissolution equilibrium. Valves 2 and 3 were then opened to allow the supercritical CO2, at the same temperature and pressure as that of the saturator, to flow through the saturator at a flow rate of approximately 0.5 mL/min for 3–5 h. The silicone resin dissolved in supercritical CO2 was then collected in chloroform in the trap bottles. Subsequently, the weight of the silicone resin in chloroform was determined by UV/Vis spectrophotometry (absorption of ~260 nm), while the total volume of CO2 passing through the saturator was measured with the gas meter. The solubility(s) of the solutes in supercritical CO2 is often expressed in mole fractions. However, since the silicone resin in this work had a molecular weight distribution, its solubility was expressed in 2 at the measured temperature and pressure was calculated from the total volume of CO2 measured at room temperature and atmospheric pressure, using the equation of state that relates the pressure, volume, and temperature of pure gases [Briefly, the procedure for measuring the solubility of the silicone resin is as follows: approximately 5 g of the silicone resin was charged into the saturator, and high-pressure COre gases . The flo2.2 was introduced into the coating vessel at a given pressure using the high-pressure pump (3). The high-pressure pump was then switched off, and the high-pressure coating vessel was closed by closing valve 2. The vessel was then stirred for 2–3 h until the coating material was completely dissolved. Subsequently, valve 3 was slightly opened and the coating vessel was depressurized at a constant rate of 0.28–2.08 MPa/min using the automatic back pressure regulator (8). After reducing to atmospheric pressure, the coating vessel was opened, and the coated ferrite fine particles were collected with a magnet.This is the apparatus in which the trap bottles and gas meter located downstream were removed from the solubility measuring apparatus in 2 into the coating vessel. The semi-flow coating procedure is as follows: a large excess of silicone resin was charged in the saturator (4) and the ferrite fine particles were loaded in the coating vessel (7); both vessels were immersed in constant-temperature water baths (5) to maintain the same temperature. Ribbon heaters (8) were attached to the lines between the saturator and coating vessel and between the coating vessel and automatic back pressure regulator (9) and were heated to the same temperature as that of the saturator and coating vessel. Subsequently, valve 2 was opened while valve 3 was closed, and the supercritical CO2 was introduced into the saturator to a given pressure using the high-pressure pump (3). Subsequently, the high-pressure pump was switched off, and the saturator was closed by closing valve 2. The vessel was then stirred for 2–3 h until the coating material was dissolved to saturation solubility. Valve 4 was then opened while valve 5 was closed, and high-pressure CO2 was introduced into the coating vessel through the blue line to create supercritical CO2 at the same temperature and pressure as that of the saturator. The coating vessel was then closed by closing valve 4 and stirred subsequently. After the supercritical CO2 dissolved the coating material to saturation solubility, valves 2, 3, and 5 were opened. While maintaining the dissolution equilibrium between the supercritical CO2 and silicone resin in the saturator, high-pressure CO2 was supplied to the saturator at a low flow rate of 0.5 mL/min using the high-pressure pump, and the supercritical CO2 with silicone resin in the saturator was driven out to the coating vessel. After charging the supercritical CO2-dissolved silicone resin into the coating vessel for a certain period (4–30 min), valves 2, 3, and 5 were closed to seal the coating vessel. The coating vessel was then stirred for 15 min until the concentration of the silicone resin in the vessel became completely uniform. Subsequently, valve 5 was opened and the pressure in the coating vessel was reduced to atmospheric pressure at a constant rate of 0.42 MPa/min, using the automatic back pressure regulator to coat the silicone resin on the surface of the ferrite fine particles. At the end of the experiment, the ferrite fine particles in the coating vessel were collected with a magnet.The thickness of the silicone resin film coated on the ferrite fine particles was measured by two methods: X-ray fluorescence analysis and cross-sectional scanning electron microscopy. The former measures the X-ray fluorescence intensity emitted from the silicon present in the silicone resin and the iron in the ferrite fine particles using a scanning X-ray fluorescence spectrometer , with film thickness determined from the silicon-to-iron X-ray fluorescence intensity ratio (Si/Fe). In the latter, film thickness was measured by observing the cross sections of ferrite fine particles before and after coating by field-emission scanning electron microscopy .2 using the flow method. Before measuring the solubilities, the relationship between the supercritical CO2 flow rate and solubility was examined to determine the appropriate supercritical CO2 flow rate. 2 in this flow rate range, because dissolution equilibrium was achieved in the saturator across the entire flow rate range. Indeed, the results revealed that supercritical CO2 flow rates ≤0.9 mL/min were suitable for measuring the solubilities of the silicone resins. To maintain dissolution equilibrium, a flow rate of 0.5 mL/min was selected in this study.The solubilities of the five silicone resins  were mea2, and 2 density and that of the vapor pressure of the solute [2 density. Moreover, the vapor pressure of the silicone resin increased with increasing temperature; however, the increment was minimal because silicone resin has a large molecular weight and two-dimensional structure. On the contrary, the density of supercritical CO2 was greatly reduced by the temperature rise in the low-pressure region. As a result, CO2 exhibited a large negative density effect, and the solubility was reduced by the temperature rise in the low-pressure region. Conversely, the decrease in CO2 density was minimal in the high-pressure region with increasing temperature. As a result, the silicone resin showed a large positive effect on vapor pressure, with solubility increasing with rising temperature in the high-pressure region. Thus, we concluded that low temperature was advantageous for realizing high silicone resin solubility under the same pressure.e solute . The sol2 molecules in the supercritical state could move and solvate the silicone resin more easily. Thus, the silicone resin with the highest number of methyl groups showed the highest solubility in supercritical CO2.2 were correlated using Chrastil’s equation [2 under the experimental temperature and pressure conditions, T is the absolute temperature F used for the least-squares method is given by:Sexp is the measured solubility, and Scal is the calculated solubility. The constants α, β, and γ were determined so that the sum of the squares of the objective function F was minimized.The solubility data for the silicone resins in supercritical COequation :(2)lnS=α2 compared to the other silicone resins, together with low environmental load, low cost, and ease of availability. Thus, S1 was selected as the coating material for the subsequent silicone coating of the ferrite fine particles using supercritical CO2.Of the five studied resins, S1 displayed a significantly high solubility in supercritical COBatch coating of the micro-sized ferrite particles with silicone resin S1 was carried out using the apparatus shown in 2 method developed in this study. Images of the entire particle, and the vicinity of the interface between the ferrite particle and silicone resin have also been shown. The ferrite fine particles coated with supercritical CO2 had thinner films than those coated by the spray drying method; however, the former method coated the entirety of the fine particles smoothly and uniformly. This was because approximately the same amount of coating material per surface area was deposited on every fine particle surface under reduced pressure, thus forming a uniform coating film.2 decompression rate was examined, and it was observed that the thickness of the coating film did not depend on the supercritical CO2 decompression rate. This observation is explained as follows: As the decompression rate changed, the deposition rate of the coating material also changed, while the deposition amount did not. Furthermore, we estimated that the ratio of deposition on the fine particles to the nucleation of the coating material did not change on altering the pressure reduction rate.The relationship between the coating film thickness and supercritical COA simple and accurate method to determine the film thickness was also developed. 2 used to dissolve the saturated coating material was studied next. 2 saturated by the coating material at 40 °C and 25 MPa. While calculating the integrated flow volume of the supercritical CO2, it was necessary to subtract 2 cm3 of supercritical CO2 in the tubing between the saturator and coating vessel because the supercritical CO2, devoid of coating material present in the tubing, diffused to the coating vessel immediately after it started flowing. In the semi-flow coating method, the coating film thickness was proportional to the integrated flow volume of the supercritical CO2 and could be adjusted by controlling the integrated flow volume. As a result, a film thickness greater than that produced by the batch method could be obtained.Using the semi-flow coating method, the relationship between the thickness of the silicone coating film and integrated flow volume of the supercritical COA calculation model for the film thickness was devised for the semi-flow coating method. The following assumptions were considered to create the model: (1) The fine particles are spheres with the same diameter. (2) The film thickness is uniform over the entire fine particle. (3) The inner wall of the coating vessel is coated to the same thickness as that of a fine particle. (4) The outflow of the coating material from the coating vessel is proportional to the inflow of the coating material to the coating vessel.The equations to calculate the coating film thickness were derived based on the material balance of the coating material in the coating vessel. The coating material flowing into the coating vessel is equal to the sum of the coating material flowing out of the coating vessel and that present on the fine particles and inner wall of the coating vessel:S of the coating material and the time integral of the flow rate F:t, Equation (5) can be expressed by Equation (6):The inflow of the coating material to the coating vessel is represented by the product of solubility dh is the diameter of the fine particle; C is the coating film thickness. The second term represents the number of fine particles, in which C/dh)2 and (C/dh)3 were negligible because the film thickness C is much smaller than the particle diameter dh. Thus, Equation (8) can be written as:The weight of the resin coated on the fine particles was calculated by the equation:dv is the inner diameter of the cylindrical coating vessel, and L is the height of the coating vessel. In Equation (10), the terms equal or greater than C2 are negligible because C is much smaller than dv and L. Thus, Equation (10) can be written as:Subsequently, the weight of the resin coated on the inner wall was calculated by Equation (10):C gives Equation (13):Introducing Equations (6), (7), (9), and (11) into Equation (4) gives:2.Equation (13) reveals that the coating film thickness is proportional to the solubility of the coating material, and the flow rate and time of the supercritical COTo calculate the coating film thickness using Equation (14), it was necessary to determine the proportional constant k in the term for the outflow amount. The coating film thickness was calculated using Equation (14), where the numerical values are given in 2 instead of conventional organic solvents was developed, and the solubilities of the coating materials in supercritical CO2 were measured to realize an environmentally friendly and high-performance coating technology. The solubilities of five silicone resins in supercritical CO2 were measured using the conventional flow method. The silicone resins showed retrograde phenomena below 24 MPa or when measured across the entire 10–30 MPa pressure range, in which higher solubilities were observed at lower rather than higher temperatures. This was explained qualitatively by the relationships between the density of supercritical CO2 and the silicone resin vapor pressure with temperature. Furthermore, the silicone resin solubility was significantly increased by replacing the phenyl groups, which occupy a large volume, with smaller methyl groups. The solubility data for the silicone resins were correlated using Chrastil’s equation, with a 5.7% average deviation between the measured and calculated results.A micro-sized particle coating technology using supercritical CO2. A new calibration curve for coating film thickness was obtained from the X-ray fluorescence analysis of the coated particle surface and the actual film thickness measured by field-emission scanning electron microscopy. This calibration curve enabled simple and quantitative evaluation of the film thickness using X-ray fluorescence data.We also examined an easy way of determining the film thickness in the fine particle coating process using supercritical CO2 was also developed. In this method, a large amount of coating material was efficiently dissolved in supercritical CO2 using a dissolving vessel capable of stirring, and the film thickness was controlled by the total flow volume of supercritical CO2 containing the coating material. A model for calculating the coating film thickness in the semi-flow coating method was established, in which the coating film thickness was expressed as a function of the coating material solubility, supercritical CO2 integrated flow volume, and charged amount of fine particles. The measured coating film thicknesses were compared with those calculated by the model, revealing good agreement with a mean deviation of 0.085 μm. This coating technology using supercritical CO2 could easily produce a uniform film with controlled-thickness and predict the film thickness accurately. Furthermore, as the semi-flow-type coating method is easy to scale up, it is expected to be applied in drug delivery and cosmetic processing.A new semi-flow coating method using supercritical CO


Fuzzy membership reflects the possibility level that the model solutions satisfy the target value and the corresponding decision risk. We further observed that the habitat area recovered by the optimization schemes of the IPFTSP model was significantly increased compared to the recommended scheme, and the increases observed were ,  and . In addition, the interval widths of the recovered habitat areas in the IPFTSP model were reduced by 17.15%, 17.98% and 23.86%, in comparison to those from the IPTSP model. It was revealed that the IPFTSP model, besides generating the optimal decision schemes under different scenarios for decision-makers to select and providing decision space to adjust the decision schemes, also shortened the decision range, thereby reducing the decision risk and the difficulty of undertaking decision schemes. In addition, the fuzzy membership obtained from the IPFTSP model, reflecting the relationship among the possibility level, the target value, and the decision risk, assists the decision-makers in planning the ecological water supplement scheme with a preference for target value and decision risk.The optimization of ecological water supplement scheme in Momoge National Nature Reserve (MNNR), using an interval-parameter two-stage stochastic programming model (IPTSP), still experiences problems with fuzzy uncertainties and the wide scope of the obtained optimization schemes. These two limitations pose a high risk of system failure causing high decision risk for decision-makers and render it difficult to further undertake optimization schemes respectively. Therefore, an interval-parameter fuzzy two-stage stochastic programming (IPFTSP) model derived from an IPTSP model was constructed to address the random variable, the interval uncertainties and the fuzzy uncertainties in the water management system in the present study, to reduce decision risk and narrow down the scope of the optimization schemes. The constructed IPFTSP model was subsequently applied to the optimization of the ecological water supplement scheme of MNNR under different scenarios, to maximize the recovered habitat area and the carrying capacity for rare migratory water birds. As per the results of the IPFTSP model, the recovered habitat areas for rare migratory birds under low, medium and high flood flow scenarios were  × 10 The wetland ecosystem is one of the most important ecosystems on earth, as it provides necessary ecosystem services such as flood control, climate regulation and habitat provision ,3,4,5,6.Owing to the complexity of the water resource management and planning systems, there exist complex information and several uncertainties, including the random variables such as flood resource and surface and groundwater availability ,12, the ILP may represent parameters and results as interval values to address interval uncertainties . As an eIn this context, in order to supplement the previous research and give consideration to interval parameter, random variable, and fuzzy variables in the system, an interval-parameter fuzzy two-stage stochastic programming (IPFTSP) model was constructed in the present study by incorporating ILP, TSP, and FMP. This IPFTSP model was subsequently applied for optimizing and adjusting the ecological water supplement scheme in MNNR under three scenarios, which shortened the scope of decision-making and reduced the decision-making risk. Another objective of the IPFTSP model was to maximize the restored suitable habitat area for the Siberian crane, oriental stork, and red-crowned crane in the MNNR. Meanwhile, the ecological and environmental benefits generated as a result of wetland restoration were taken into account and regarded as important constraints of the model. The results presented herein provide suggestions to managers for recovering wetland areas, protecting rare migratory water birds and their habitats, and formulating reasonable scientific optimization schemes for ecological water supplement.Because of the complexity of the lake topography, the longitudinal profile of the lakes in MNNR was assumed to be a regular parabola to simplify the water level–area–volume relation curve. Moreover, the calculated function of the relationship coefficient between the suitable habitat area and the water volume was complex, but monotonically decreasing. In addition, the amount of water replenishment was limited, so the minimum value of the relationship coefficient was chosen to simplify the calculation. On the basis of the mentioned assumptions, fuzzy mathematical programming was added to the base of the IPTSP model, and the area of ecological function regions and the total planning area of lakes were set as fuzzy variables in order to obtain optimal solutions under further relaxed conditions. The fuzzy variables set in this study conform to the semi-trapezoidal membership function, defined as follows:The objective function of the IPFTSP model is presented below:(1)i represents the lakes in MNNR; i (ha/104 m3); i (104 m3); h represents the flood flow scenario;h, and i under scenario h (104 m3). 3 ha).The constraint for the maximization of the recovered habitat area is presented below:ake i ha/4 m3; QTi(2)j denotes the ecological function region, and 3 ha); and j of lake 4 m3/103 ha).The constraint for minimum water demand is as follows:(3)i under scenario h, respectively (104 m3); 4 m3); n represents the water intakes in MNNR; i under scenario h (104 m3); 4 m3) [The constraints for water supply capacity are as follows :(6)QTi±−(4)j of lake i (103 ha). The constraints reflect that, in the project recommendation scheme, the fish and crab ponds are prioritized over the reed and marsh wetlands, while reed wetlands are prioritized over the marsh wetlands.The constraints for water supplement sequence in different ecological function regions are as follows:(5)i (103 ha), while j of lake i (103 ha).The constraints for the area of ecological function regions are presented below:(6)k represents ecological service functions of MNNR; k of ecological function region j (106 CNY/103 ha); k generated by the project recommendation scheme (106 CNY) [The constraint for the ecological benefits is presented below :(19)∑i=1(7)j (t/103 ha); i generated by the project recommendation scheme (t) [The constraint for the net carbon sink is as follows : (20)∑j=gion j t/3 ha; TCSConstraints:In the present study, the parameters used to determine the solution of the IPFTSP model were consistent with those used to determine the solution of the IPTSP model in a previous study . Data oniQT, In order to determine the solution of the IPFTSP model, the objective function of the IPTSP model  is the largest wetland reserve of Jilin Province, with a total area of 14.4 × 10By solving the IPFTSP model, the fuzzy membership interval was obtained as 4 m3 (the first-stage decision), with a decrease of 5.56% compared to that of IPTSP model, which is conducive to reducing water use [4 m3,  × 104 m3, and  × 104 m3, respectively. Furthermore, the water shortage (the second-stage decision) is calculated as the difference between the actual water supply and the optimal target of water supply. The water shortages under low, medium, and high flood scenarios were determined to be  × 104 m3,  × 104 m3, and  × 104 m3, respectively, demonstrating that the optimal water supply targets under the three scenarios were not fulfilled. When the water shortages under different scenarios were compared, it could be observed that, with the increase in flood flow, the water shortages at different water intakes decreased gradually, while the total amount of optimal water supplement continuously increased. This observation demonstrated that the developed IPFTSP model was capable of effectively optimizing and adjusting the ecological water supplement scheme recommended by the project, and could completely utilize the limited water resources and avoid wastage of water resources under various scenarios. As shown in ater use . The actThe optimization of the ecological water supplement scheme gave priority to the supplement of flood resources and improved the utilization of flood resources. In the total actual optimal water supplement, the proportions of flood resource supply under the three different scenarios were 27.49%, 29.05%), 33.85%, 36.87%), and , respectively. In addition, the proportion of flood resource supply increased with the increase in flood flow, indicating that complete utilization of the flood resources under various scenarios could meet the water demand of MNNR and alleviate the water shortage to a certain extent . Further%, 29.05%.87%, and4 m3, 2097.62 × 104 m3, and 2787.10 × 104 m3, respectively. In addition, the upper bound values of the total available water were greater than the optimal target of water supply by 386.85 × 104 m3, 1421.08 × 104 m3, and 2110.56 × 104 m3 under the three different scenarios, respectively, although water shortages nonetheless remained. This observation is mainly because the scope of planning in the case of the lakes in MNNR is limited and cannot be expanded indefinitely, and consequently, the acceptable amount of the ecological water supplement is also limited. The optimal water supply targets of certain lakes corresponding to the BIA were greater than the acceptable ecological water supply, leading to water shortage even when the water supply was adequate. Therefore, the optimal water supply targets of these lakes require adjustment. At the same time, the upper bound value of the total available water was higher than the optimal water supply target, which also indicated that the system had a strong capability to meet the actual optimal water supply, causing the risk of system failure to be relatively low. The same law is also reflected in the ZPS. Under the three different flow scenarios, the total available water was equal to the actual water supply in the lower bound sub-model, while the upper bound sub-model had a small surplus water resources. In the case of the SIG, the optimal water supply target could only be met under the medium and high flood flow scenarios in the upper bound sub-model, with a water surplus of 141.00 × 104 m3 and 669.31 × 104 m3, respectively. The optimal water supply target of the HPS could be met only under the scenario of high flood flow in the upper bound sub-model, with a water surplus of 43.49 × 104 m3. Overall, under the three flood flow scenarios, the ecological water supplement in the lower bound sub-model was inadequate, and was required to be increased, while there was a water surplus of 1201.75 × 104, 2376.97 × 104, and 3659.03 × 104 m3, respectively, in the upper bound sub-model. It is recommended to direct the surplus water toward other regions with water demand in order to avoid wastage of water resources.In comparison to the IPTSP model , the FMPUsing ecological water supplement optimization schemes under different flood flow scenarios and the relationship coefficients 3 ha, with a possibility level of , which reflected the level of system failure risk. Under the three flood flow scenarios, the recovered habitat area values obtained through the upper bound model scheme were 17.88 × 103 ha, 18.96 × 103 ha, and 19.43 × 103 ha, while the target value was 18.47 × 103 ha, with a possibility level of 0.83 that indicated a high level of system failure risk. The recovered habitat area values obtained through the lower bound model scheme were 14.06 × 103 ha, 14.92 × 103 ha, and 15.83 × 103 ha, while the target value was 14.60 × 103 ha, with a possibility level of 0.01, which indicated a significantly reduced risk of system failure. In other words, if a decision-maker selects the target valve of 18.47 × 103 ha at a probability level of 0.83, it presents a high risk in the corresponding decision scheme; in comparison, if the decision-maker selects the target valve of 14.60 × 103 ha at a probability level of 0.01, it sharply reduces the risk in the decision scheme. As stated earlier, fuzzy membership reflects the possibility that the model scheme fulfills the fuzzy objectives and constraints , which a3 ha with a possibility level of 0.16, while the target value determined for situation 3 was 18.02 × 103 ha with a possibility level of 0.74. In this case, when the lower bound value of the target value in situation 1 was compared with that of the target value in situation 2, it was observed that the target value in situation 2 was larger and the corresponding possibility level had also increased. This could be attributed to the increase in the flood resources, because of which the scheme of situation 2 exhibited a higher capability of meeting the target value and constraints, resulting in a greater target value and a higher possibility of satisfying the target value and constraints. However, the increase in flood resource utilization would also present a higher level of system failure risk, i.e., the demand for flood resource utilization cannot be met. The same law might be observed while comparing the target value in situation 3 with the upper bound value of the target value in situation 1. In situation 3, the utilization of flood resources was reduced, and a part of the target value was sacrificed in order to reduce the level of system failure risk. The fuzzy membership assists the decision-makers to tradeoff the relationship among the target value, the risk level, and the possibility level during the formulation of the preferred water supplement scheme.The model target value and fuzzy membership would vary within their intervals as the parameters in the IPFTSP model are adjusted within the interval . Clarify3 ha in the project recommendation scheme. Under different flood flow scenarios, the habitat area recovered through optimal water supplement schemes exhibited improvement in comparison to that in the recommended scheme, with the increases of , , and  at the scenario probabilities of 50%, 38%, and 12%, respectively. In addition, the recovered habitat areas under the scenarios of medium and high flood flow were significantly increased by  and , respectively, compared to that under the low flood flow scenario. After optimizing allocation through the IPFTSP model, the increased water resources observed with the increase in flood flow could be utilized effectively, which could alleviate water shortage as well as increase the recovered habitat area for rare migratory water birds under the different scenarios, with significant optimization effect. Locally, the size relationship of the recovered habitat area in different regions under the different flood flow scenarios was as follows: r = 1 > r = 2 > r = 3 > r = 4. In addition, under the three flood flow scenarios, the upper bound values of the habitat area recovered through optimal water supplement schemes exhibited improvement in all the regions in comparison to the corresponding values in the recommended scheme, while the lower bound values of the recovered habitat area in regions 2 and 4 exhibited a relative decrease. This was mainly because of inadequate water supply in regions 2 and 4 in the lower bound sub-model, and it is, therefore, recommended to divert water from other places to these regions. The suitable habitat area recovered through the ecological water supplement schemes optimized using the IPFTSP model increased, compared to the ecological water supplement recommended by the project. As shown in The Siberian crane, oriental stork, and the red-crowned crane migrate to MNNR in the autumn season (from early September to early October), where they rest for 1 to 2 months . Thus, t3,  × 103, and  × 103 birds, with the increase of , , and , respectively, compared to the recommended scheme. These increased proportions clearly indicated that the ecological water supplement scheme optimization was capable of improving the carrying capacity for rare migratory water birds in MNNR, which would facilitate the recovery and expansion of the populations of rare migratory water birds; this has important implications in the safety of endangered and rare species of migratory water birds such as the Siberian crane [Using the distribution density of the study species and the recovered habitat area in each lake, it was possible to determine the carrying capacity of MNNR for the study species. The carrying capacity for the study species recovered through the optimization schemes under the different flood flow scenarios was  × 103,  × 103, and  × 103 birds, with increases of , , and , respectively, compared to the project recommendation scheme. The comparison of the recovered habitat area and the carrying capacity for rare migratory water birds between the IPTSP and IPFTSP models revealed that under different flood flow scenarios, the upper bound values of the recovered habitat area and the carrying capacity in the IPFTSP model were smaller than those in the IPTSP model, while the lower bound values were all greater than the corresponding values in the IPTSP model. This was because the IPFTSP model adds a fuzzy programming method to the base of the IPTSP model, which is capable of completely considering the fuzzy uncertainty of the area of the ecological function region and total planning area of the lakes, and then optimize the constraint conditions through membership relationship, thereby increasing the lower bound values and reducing the upper bound values of the recovered habitat area and the carrying capacity obtained earlier in the IPTSP model. The recovered habitat area and carrying capacity for rare migratory water birds are consistent parameters. Therefore, the influence of fuzzy mathematical programming on the optimization schemes could be analyzed through a comparison between the IPFTSP and IPTSP models in terms of the recovered habitat area and the carrying capacity for rare migratory water birds. The interval width of the target value in the IPFTSP model was smaller than that in the IPTSP model . In the sk level .3 ha,  × 103 ha, and  × 103 ha, with the changes of , , and , respectively, compared to the recommended scheme. The ecological water supplement in MNNR would be accomplished before the arrival of the rare migratory water birds. Therefore, the increase of water surface area was beneficial to increase the suitable habitat area of rare water birds. In addition, the water supplement originates from the Nenjiang River, and a large amount of fish, crabs and other foods would be carried in the water supplement, which provided abundant food resources for rare water birds. The larger area of lakes and wetlands as well as abundant food resources were conducive to the survival of rare water birds, which would attract more rare water birds. Among these increases, the lower bound value of the recovered water surface area exhibited a great increase, while the upper bound value either increased slightly or remained unchanged. The restoration of water surface area has a close association with the ecological water supplement. Since the ecological water supplement in the lower bound sub-model under different scenarios is inadequate, the recovered water surface area increases significantly with the increase in water supplement. On the contrary, the water supplement in the upper bound sub-model under the three flow scenarios is relatively sufficient with just small differences, and the area of the fish pond and crab pond is limited, which results in either a small increase or no increase at all in the upper bound value of the recovered water surface area. Ecological water supplement is an important and efficient approach for the restoration of wetlands . The ecoScirpus planiculmis for rare water birds. The recovered wetland areas under the three flood flow scenarios were  × 103 ha,  × 103 ha, and  × 103 ha, with the changes of , , and , respectively, compared to the recommended scheme. It was observed that the lower bound value of the recovered wetland area under the three flood flow scenarios was smaller than that of the recommended scheme. After analysis, the main reasons identified for this were as follows: (1) in the order of water supplement priority, the fish and crab ponds came prior to the wetlands, and therefore, under the condition of inadequate water supplement, the water demand of the water surface area needs to be satisfied first; (2) the ecosystem service value per unit area of fish and crab ponds is higher than that of the wetlands, while the ecological water demand per unit area of the ponds is lower than that of reed wetland, which implies that in the case of insufficient water supply, supplying more water to fish and crab ponds is conducive to enhancing the overall ecological service value of the system. The changes in the recovered wetland area under the scenarios of medium and high flow were  and , respectively, compared to that under the low flood flow scenario, which implies that the lower bound value of the recovered wetland area under the medium flow scenario is lower than the corresponding value under the low flow scenario. This could be attributed to the fact that the water demand per unit area for reed wetland is greater than that for the crab pond and the marsh wetland, while its ecosystem service value per unit area is less than that of the crab pond. Therefore, based on increasing the area of marsh wetland in order to satisfy the constraint for net carbon sink, appropriate reduction in the reed wetland area in the case of inadequate water supplement is conducive not only to increasing the ecosystem services value but rather also to increasing the total restoration area.The restoration of larger wetland areas (reed and marsh wetlands) could provide more nesting sites and sufficient food resources such as bulbs of 3 ha in the recommended scheme, the lower bound values of the total area of the function region recovered through IPTSP and IPFTSP models were smaller (in both models), while the upper bound values were greater. This could be mainly attributed to the characteristics of the interval-parameter method used. The lower bound value is obtained under the worst conditions , and the water supply is inadequate, resulting in smaller lower bound values of the total recovered area of the function region in the IPFTSP and IPTSP models compared to those in the recommended scheme. In the IPFTSP model, the total recovered areas of 38.23 × 103 ha, 40.82 × 103 ha, and 41.78 × 103 ha under different scenarios were obtained at a probability level of 0.83, which reflects a high degree of satisfaction for the managers although with a high level of system failure risk. On the other hand, the total recovered areas of 29.31 × 103 ha, 31.31 × 103 ha, and 33.57 × 103 ha under different scenarios were obtained at a probability level of 0.01, which reflects a significantly reduced risk of system failure and an extremely low degree of satisfaction for the managers. In 3 ha, 3.32 × 103 ha, and 4.26 × 103 ha, respectively. This led to a significant reduction in the interval width of the total recovered area in the IPFTSP model compared to that in the IPTSP model, and the reduction ratios under the different scenarios were 23.52%, 26.48%, and 32.54%, respectively  model was constructed through the addition of fuzzy mathematical programming to the base of interval-parameter two-stage stochastic programming (IPTSP) model, with the aim of effectively addressing the interval parameters, random variable, and the fuzzy variables in the system simultaneously, to narrow down the decision-making scope, ultimately reducing the decision-making risk. In addition, the constructed IPFTSP model was applied for the optimization and adjustment of the ecological water supplement scheme in Momoge National Nature Reserve, with the objective of obtaining maximum recovered habitat area for the Siberian crane, oriental stork, and red-crowned crane, and for generating better ecological service value and net carbon sink. This study demonstrated that the constructed IPFTSP model could reasonably utilize water resources under different flood flow scenarios, thereby resolving the issue of wastage of water resources in the case of sufficient availability of water resources. This was well reflected in the results when the recovered habitat area and the carrying capacity for rare migratory water birds were observed to increase with the increase in flood flow. In addition, the upper bound values of the recovered habitat area and the carrying capacity under different flood flow scenarios were obviously larger than the lower bound values, offering decision-making space to the decision-makers for adapting the ecological water supplement optimization scheme to the actual requirements. In contrast to the IPTSP model, the added FMP method reduced the overall decision-making range of the IPFTSP model by 18.28%, leading to a significant reduction in the upper bound values of the ecological service value, the net carbon sink, the recovered area of the water surface and the wetlands, the recovered habitat area, and the carrying capacity for rare migratory water birds in the IPFTSP model, which was achieved with a reduced system risk of not being able to reach the upper bound values in the model result in practice. In addition, the reduction in the decision–making scope in the IPFTSP model brings the model results closer to the actual situation and reduces the decision-making risk, which assists the managers in undertaking reasonable decisions conveniently. Moreover, the obtained fuzzy membership of the IPFTSP model reflected the relationship among the target value, the possibility level, and the risk level, which could provide decision support to the decision-makers for formulating the water resource management scheme with a reasonable target value and an appropriate risk level. The increase in the numbers of rare migratory water birds would be conducive to the study of their ecological habits and migration rules, which is another among the important significances of the present study. Scirpus planiculmis were not directly considered in this study. In addition, certain assumptions were made during the calculation of the relationship coefficient between the suitable habitat area and the water volume, and some proportional relationships were assumed in the calculation of the upper and lower bound values of ecological service value per unit area and net carbon sink capacity. These limitations would lead to systematic errors and limited usability of the model. Therefore, further investigation regarding the restoration and improvement of the suitable habitat area and the carrying capacity for rare migratory water birds is warranted.Despite the promising results, the present investigation has certain limitations. One limitation is that besides water depth and potential food resources, no other factors such as total wetland area, total water surface area, and human disturbances were taken into consideration while defining the suitable habitat area for rare migratory water birds . This is


In patients with high myopia, a weak negative correlation between ET-1 concentration and the longest axial length out of the two eyes was found . Further analysis revealed statistically significant differences in ET-1 concentration between patients with the axial length of the eye > 26 and ≤ 26 mm (p < 0.041) and patients with the axial length of the eye > 26 mm and controls (p < 0.001). ET-1 expression is disturbed in highly myopic children and adolescents. Lower ET-1 concentration in patients with the axial length of the eye > 26 mm may co-occur with high myopia and should be considered a risk factor in the pathophysiology of high myopia progression.The aim of this study is to evaluate the levels of enothelin-1 (ET-1) in children and adolescents with high myopia and its association with the axial length of the eye and the presence of myopic retinal degeneration. The cross-sectional study was carried out in 57 patients with high myopia and 29 control subjects. Serum concentrations of ET-1 were measured using enzyme-linked immunosorbent assay (ELISA) kit. A significantly lower concentration of ET-1 in highly myopic patients compared to controls was found  vs. 1.94  pg/mL,  Myopia is one of the most common eye disorders in the world and its prevalence remains higher in Asia (60%) compared with Europe 40%). Studies report high prevalence rates in schoolchildren in East Asia 73%) and North America 42%). Low prevalence below 10% has been demonstrated in African and South American children. Risk factors for myopia in schoolchildren include limited outdoor time, dim light exposure, use of LED lamps for homework, insufficient amount of sleep, reading distance less than 25 cm, and living in an urban environment .In subgroups of patients, taking into account the axial length of the eye ≤ 26 and > 26 mm, statistically significant differences between means of refractive errors of right and left eyes were observed [−6.9 ± 1.7 (−11–−4.3) vs. −8.5 ± 3.2 (−18–−3); In the current study we concluded that endothelin-1 (ET-1) expression is disturbed in children and adolescents with high myopia. The significantly lower concentration of ET-1 observed in patients with the axial length of the eye > 26 mm, both male and female, in comparison to myopia patients with the axial length of the eye ≤ 26 mm and to the controls may indicate disturbance in the endothelin signaling pathway and its role in the pathophysiology of high-myopia eyes. A weak negative correlation between ET-1 concentrations and the longest axial length out of the two eyes, and a strong negative correlation between the axial length of the eye and SE refractive error in both eyes suggest an association between lower ET-1 concentrations and severity of high myopia. Low serum ET-1 levels in our study may co-occur with high myopia and may be due to insufficient expression or rapid elimination processes of ET-1. Circulating ET-1 is mainly eliminated in the lung. The primary mechanism of elimination in the lungs and liver is by the internalization of the ETB (ETA) receptor and ET-1 complex, whereas in the kidneys by degradation by neutral endopeptidase  . To the Myopia is the most common eye disorder in children and adolescents. It is a condition in which individuals can see close objects clearly, while objects that are farther away appear blurred. In most cases, this condition occurs when the eyeball is too elongated, relative to the focusing power of the cornea and lens of the eye. This causes the light rays to focus at a point in front of the retina, not directly on its surface. In some cases, the eyeball is much more elongated, and this condition is called high or pathological myopia. Less commonly, myopia can also be caused by the cornea and/or lens being too curved for the length of the eyeball. In some cases, myopia occurs because of a combination of these factors. Myopia is a complex disease with a multi-factorial etiology. Many experimental and clinical studies have shown that myopia development results from the interplay between genetic and environmental factors ,16. NumeThere is increasing evidence that the endothelin signaling pathway plays a key role in the pathogenesis of several ocular diseases and ET-1 level is a useful marker for evaluation of intraocular hemodynamic. The amount of blood needed in various organs and tissues varies and is achieved by adapting perfusion pressure and local resistance, for which the diameter of vessels is responsible . In the 2 to 70 dyne/cm2. Such shear stress exerts a protective effect on the vascular endothelium by stimulating the production of vasodilators. The thickening of the inner membrane occurs in places where wall shear stress is less than 10 dyne/cm2. Experimental studies using flow chambers have shown that the endothelium already responds to very small changes in the shear stress value [Reduced saturation of arterioles in the retina as well as narrowing of the retinal vascular diameter in highly myopic eyes has been previously demonstrated ,25,26,27ss value . All thiThe two major limitations of our study were the small sample size and the observational design of the study. This did not allow us to draw firm conclusions about causality. In addition, the inability to assess the concentration of factors known to promote the expression and inhibitors of ET-1 in this study may limit the spectrum of possible associations.In spite of the limitations of the study, we found that the expression of endothelin-1 is disturbed in high myopia pediatric patients with the axial length of the eye > 26 mm, and the lower level of ET-1 may co-occur with high myopia and may play a role in chorioretinal circulation and in the pathophysiology of high myopia progression. Therefore, the assessment of ET-1 levels in patients with high myopia may provide additional insights into choroidal and retinal hemodynamic and to the development of new therapeutic strategies to prevent myopic blindness. However, further studies involving a larger number of participants and longer follow-up duration are required to confirm our results.


The article deals with the issue of determination of the content of SBS (Styrene-Butadiene-Styrene) in polymer-modified bitumens (PMBs). The effect of SBS copolymer on the physical and rheological properties of bitumens has been thoroughly investigated and widely described in the literature. Condition surveys of structures and evaluation of the properties of materials used at construction sites have become a huge challenge for construction engineering. Determination of the content of SBS modifier in various building materials  is a good example in this respect. Based on the laboratory tests, mid-infrared spectroscopy was found to be the most effective analytical method. It can be used for easy detection of the presence of SBS in a modified bitumen. However, quantitative analysis is an issue that calls for research. Currently, there are no standard guidelines, whether national or European, that would regulate the method of testing. Three test methods were assessed in this study: the AASHTO T302–15 standard method and two Australian methods described in codes of practice (T521 and Q350) developed by the local authorities, which define a standard way of determining the amount of SBS in polymer-modified bitumens. The tests were carried out on standard controls and samples sourced from the industry. The above-mentioned test methods were assessed in terms of accuracy of determination, reliability of results obtained on the industrial samples, level of complexity of the test procedure, sample preparation techniques and the type of the required reagents. Bitumen became a popular building material quite recently, namely at the beginning of the 20th century and already at that time the first modification attempts to improve its performance were made ,2,3. SysThe present state of engineering knowledge makes it possible to precisely design a civil structure or manufacture a material with the desired properties. Currently, research efforts are focused on the issues related to condition assessment of structures and evaluation of the properties of construction materials available on the market. To build or make something is no longer a problem for an engineer. Conversely, to find out what that something was made of is still a challenge. In this respect, our research concerned the determination of the percentage content of SBS in polymer-modified bitumens used to produce a specific HMA and waterproofing compound. As follows from various laboratory studies ,29,30,31Neither the European Standards nor national codes provide a standard test method for determining the content of SBS in polymer-modified bitumens. In this study, we assessed the effectiveness of the above-mentioned methods through multi-criteria evaluation. The primary evaluation criterion was the accuracy of measurement and the reliability of the results obtained for the industrial samples. The complexity of the test procedure, sample preparation technique and the type of reagents needed to carry out the test were also analyzed.The laboratory testing part of this research was carried out in two stages. In the first stage, in-house samples were used, prepared by modification of base bitumens with different amounts of SBS. In the second stage, the developed methods of determination of SBS content in modified bitumens were verified through testing of industrial samples. The samples were obtained from commercial asphalt mixing plants, which used polymer-modified bitumens for the production of asphalt mixtures. In the first stage, the base binders were paving bitumens 160/220 and 50/70. These bitumens were produced by PKN ORLEN S.A.  from crude oil coming from the Ural oil fields. They are widely used in the production of waterproofing and paving materials. The main properties of these basic bitumens are compiled in This was reflected in the values of the colloidal stability index (GI), which were 0.31 in the case of bitumen 160/220 and 0.48 in the case of bitumen 50/70. Based on the literature review, the value of GI = 0.36 is considered the limit value [TM D1101 A Polymer, an SBS with a linear structure, manufactured by Kraton Corporation . The main properties of SBS used in this study are given in TM D1101 is one of the most widely used polymers in the Polish building materials market. The test results presented in this paper are the first part of research project. In the next stage, different types of SBS and bitumen from different sources will be tested to evaluate the considered test methods.The base bitumens were modified with KRATON®-Werke GmbH & CO. KG, Staufen, Germany), equipped with a special dispersing tool, was used. The instrument offers speed range up to 25,000 rpm and can handle high viscosity materials of up to 5 Pa·s.Bitumens 160/220 and 50/70 were modified by addition of 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 6%, 8% and 10% of SBS by weight. The method of preparation of lab samples is depicted in the schematic in In the second stage of the laboratory tests, five types of polymer-modified bitumens used in HMA production were tested: three classified as polymer-modified bitumens (PMB) and two belonging to the highly-modified asphalt (HiMA) group. For each bitumen type, the tests were done on samples of fresh binder, binder subjected to simulated short-term ageing according to EN 12607-1 (RTFOT)  and bindThree test methods were applied for determining the content of SBS in polymer-modified bitumens, which were then assessed by the application of the criteria including accuracy of measurement, complexity of the test procedure, sample preparation technique and harmfulness of the reagents.−1 wave number (A1) was considered indicative of the presence of SBR, SB or SBR with the base bitumen peak at the wave number of 1375 cm−1 (A2). The first of the assessed methods is described in the code of practice No. T302–15 (2019)—Standard Method of Test for Polymer Content of Polymer-modified Emulsified Asphalt Residue and Asphalt Binder  developeThe C/H ratio of bitumen is constant.2 functional group is taken as a standard.The band of the CH−1, respectively, are indicative of the presence of SBS and SBR modifiers, yet without discriminating them.Bands 1 and 2 at wave numbers 700 and 970 cm−1 (1) can be indicative of the presence of any mono substituted aromatic compound. The simultaneous presence of Bands 1 and 2 (700 and 970 cm−1) is very strong evidence of the presence of styrene-butadiene copolymer combined at a 30:70 ratio (note that lab samples were modified with SBS containing 30–32% styrene).In principle, a band at 700 cmThe second assessed test method is described in the code of practice No. T521 Quantification of polymer-modified binders using infrared spectrum , issued −1. It should fall in the range of 5–30%. A transmission rate higher than 30% indicates that the residual film is too thin, and another drop must be applied on the disc. If the transmission rate is below 5%, this means that the residual film is too thick and a new sample must be prepared. Determination of the concentration of SBS or SBR in PMBs is based on analyzing three characteristic peaks for wave numbers 700 (1), 970 (2) and 1380 cm−1 (3), respectively. To each of these peaks, tangential base lines are drawn for the following bands:−1—for peak at 700 cm−1690–790 cm−1—for peak at 970 cm−1930–1130 cm−1—for peak at 1380 cm−11230–1400 cmThe samples were prepared by heating them to 175 ± 5 °C according to EN 12594 . After snPeak) and for the plotted baseline (nLine) at the same wave number with an accuracy to 0.5% and the value of nA was calculated using the following formula:nA is the result for a given band n; nLine is the baseline transmission value %; nPeak is the bsolute transmission value in percent; and n is the band number, with 1 = band 690–790 cm−1, 2 = band 930–1130 cm−1 and 3 = band 1230–1400 cm−1. nA.Next, the percent transmission was read for each peak . The vial was then placed in a mechanical shaker and shaken for at least 1 h at room temperature. Using a dropper, two drops of the solution taken from the upper part of the vial were transferred onto a glass plate in a fume hood, minimizing the diameter of the resulting spot as far as practicable. Next, the glass plate was left to allow the solvent to evaporate. This sequence was repeated until adequate thickness of the film was obtained (ca. 5 mm diameter of sample and thickness sufficient to block the passage of light). The sample was then placed for 1 h in a drying oven heated to 40 °C. The measurement of mid-infrared spectrum was carried out through the ART method with the test setup parameters given in The third assessed test method is described in the code of practice No. Q350: SBS content of polymer-modified binder  developen is the peak area for the wave number n.The percentage of SBS was calculated using the following formula:2. The results obtained for the industrial samples are given in 2 was close to 1. A small variability was noted in the SBS contents measured on the industrial samples  or binder recovered from HMA. The mean SBS contents were 3.6%, 3.8% and 3.1% for bitumens A45/80-55, A45/80-65 and B45/80-55, respectively. In the case of HiMA bitumens, the mean SBS contents were 4.5% and 5.2% for bitumens C45/80-80 and D45/80-80, respectively. In contrast to the results obtained with the procedure described in T302–15, here a difference between PMB and HiMA binders is evident.In addition, the industrial samples  did not 2 were 0.75 for bitumen 160/220 and 0.54 for bitumen 50/70. In the case of industrial samples of PMBs . This method utilizes the height ratio of the polymer and binder peaks and is characterized by simple measurement and data analysis techniques. The most time-consuming part of the process is preparation of the test specimens, comprising preparation of bitumen solution and the discs on which it will be applied. However, simplification of this method by use of ATR  and analysis of peak areas instead of peak heights results in considerable measurement errors in determination of the actual SBS copolymer content. Moreover, the results obtained on the industrial samples raise doubts due to the lack of a clear difference in the content of the modifier between PMB and HiMA binders.The biggest measurement error was observed in the case of the results obtained according to the procedure described in the Q350 code of practice. In addition, it involves the most time-consuming preparation of samples and the use of carbon disulfide as a solvent, which is a toxic chemical compound, harmful to the central nervous system and has potential for carcinogenic and mutagenic effects. Large measurement errors are caused by the utilization of ATR and determination of the SBS percentages on the basis of peak areas. This is the only method based on the use of as many as four different bands, which might imply measurement errors. However, marked differences in the experimental determinations of SBS percentages in PMB and HiMA are worth noting in this case.−1 wave number (indicative of the presence of SBS) introduced in the spectral analysis in this method increased the mean measurement error in the case of laboratory samples, the considerable difference between the results obtained for PMB and HiMA binders, testifying to its performance and efficiency, can support the choice of this procedure.In the T521 method, the mean error of measurement obtained on the lab samples was 0.66%, which was slightly higher than the mean error obtained in the method T described in AASHTO T302–15. Transmission mode of measurement and peak heights are used also in the T521 method and the difference is in the preparation of samples, which involves the use of a different solvent (THF or Toluene). Although an additional band of 690 cmLaboratory determination of the content of SBS copolymer in PMBs is usually performed on samples obtained from the industry with the purpose of assessing the quality of the applied construction materials. It is quite rare that in-house controls can be prepared using fresh binder and its own standard curve be derived. The T302–15 test method with transmission mode yields very satisfactory test results for lab samples, but with industrial samples no differences between PMB and HiMA were observed, which is questionable. The Q350 and T302–15 ATR test methods are characterized by a high mean error value. The T521 test method has satisfactory value of the mean error and the test results for industrial samples are reliable Therefore, in view of the above, the measurement technique described in the T521 code of practice is considered to be the most optimal choice among the methods analyzed in this study.


In order to process micro scale parts more conveniently, especially the micro parts with complex shape, a new micro blanking equipment based on piezoelectric ceramic driving is proposed in this paper. Compared with other large precision machining equipment, the equipment cost has been greatly reduced. Using displacement sensor to detect the change of output displacement and feedback control piezoelectric actuator to control the change of relevant parameters, the control precision is high. The micro gear parts with diameter less than 2 mm are obtained through the blanking experiment on the experimental equipment. From the relationship between the obtained time and the punch output force, output displacement and die adjustment, it can be seen that the designed equipment has good processing performance and can complete the blanking forming of micro parts well. The miniaturization of industrial equipment, especially medical equipment and electronic equipment, is to meet the requirements of the development of modern medical science and precision instruments, so the components of these equipment must be more miniaturized and high-precision. For these micro scale parts, different from traditional size parts, special processing methods must be used. For example, laser dynamic flexible punching process, electrical-field activated sintering, metal powder compaction in elastic dies, and micro wire electrical discharge machining are the common processing methods studied at present ,2,3,4. Fn is the number of piezoelectric ceramics,u is input voltage, t is the thickness of each piezoelectric ceramic, n = 27. The deformation of single-layer ceramic is limited. In this project, the piezoelectric ceramic driver is designed by stacking multi-layer piezoelectric ceramic, as shown in The relevant values of die root diameter and punch tip diameter are listed in F2, the punching force F1 and the counter pressure F3 at the same time.The stress during precision blanking is shown in F1 can be calculated by Formula (2):The blanking force t is the workpiece thickness;l, the involute length of one-side of gear teeth is calculated first [In order to get the contour length ed first , and itsd;The tooth thickness on different circles is calculated as Formula (4) ,27:(4)φds is the tooth thickness of graduation circle;r is the radius of reference circle;d;z is teeth number of the gear;The total length of contour circumference is obtained as Formula (5):Comprehensive of Formulas (3)–(5), the calculation results of the total length of contour circumference are as follows:t, f1 and F1 is:Substituting h is v-shaped tooth height of blank holder.The calculation method of blank holder force can be obtained from the empirical formula of Reference :F2=f2lt2F3 will have an impact on the dimensional accuracy, flatness, collapse angle and the quality of the shear plane of the workpiece. Increasing the back pressure appropriately will improve the above indexes, but excessive back pressure will increase the punch load. Back pressure of fine blanking process can be calculated by Formula (6) [p is unit back pressure, generally taken at 20~70 N/mm2, with p = 55 N/mm2; A is the end area of part; the calculation formula can be obtained from Reference [The value of the back pressure mula (6) :(6)F3=pAeference .(7)A=, we can obtain:The total pressure required by the workpiece to finish the fine blanking process is the main basis for the design of stamping equipment. The workpiece should be blanked before fine blanking to ensure reliable blank pressing. The total pressure includes blanking force and back pressure, which can be calculated as follows:We used Solid Edge software to build 3D model and save it in STL format. Then, we imported STL file into DEFORM software and adjusted the position of each part to form the original model as shown in There are three hundred steps in the whole simulation process. The effective strain of blank is shown in A set of device for precision forming of micro parts based on piezoelectric ceramic driver is developed. (1) Through the displacement sensor detection and feedback, the position adjustment of the precision electric displacement table is realized, so as to complete the adjustment of the machining position of the parts. (2) The control system of the device is designed. By selecting the appropriate control parameters, the device can run stably and reliably. (3) The tooth profile of the micro gear is clear, and the microhardness meets the requirements of the gear, so the designed micro stamping system can form the micro parts with good quality.


The number of nickel hydroxide particles required to form one nickel nanoparticle was estimated, and a model of its formation was proposed.In this study, the mechanism of nickel nanoparticle formation from its hydroxide was analyzed. Metallic nickel nanoparticles were obtained through the hydroxide’s reduction under hydrogen. Nickel hydroxides were produced from nickel (II) nitrate hexahydrate and NaOH by deposition under various initial conditions. The influence of washing treatment on the dispersion of obtained nickel powders was studied. The washing procedure of precipitates was carried out by centrifugation, ultrasonic treatment, and decantation. X-ray diffractometry, transmission electron microscopy, low-temperature nitrogen adsorption, infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy methods were used for nanoparticle characterization. Based on the resulting data, a model of the Ni(OH) In the last decade, the preparation and use of nanomaterials have been two of the most promising areas of scientific research due to the unique properties of nano-sized structural components ,2,3. NanNickel-based nanoscale powders have attracted the interest of researchers due to their good catalytic, magnetic, and tribological properties ,8,9,10. Currently, the lack of understanding of a new phase formation mechanism is one of the major problems in the control of nanomaterial dispersion. The reduction process is used for obtaining metallic nanoparticles, with the “shrinking core” being the most common model used to describe the formation mechanism of the metal phase during the reduction process ,19,20. AThe current research investigates an application of the “shrinking core” mechanism to nanomaterial formation. Metallic nanoparticles have been objects of research for many years, but the processes that occur during their formation are still understudied. Though there is a multitude of chemical methods available for nanoparticle production, the issue relating to dispersion and particle shape control is still unsettled. Hence, the purpose of this research is to determine the mechanism of nickel nanoparticle formation and its influence on their dispersion. The synthesized nickel nanoparticles are considered an addition to metal powders for additive manufacturing. Three-dimensional printing, as a frontier manufacturing technique, enables the rapid production of complex geometry components with unique and highly tailorable microstructures ,26. HoweThe original reactants used for nickel hydroxide production were nickel (II) nitrate hexahydrate  and NaOH alkali . The nickel hydroxide powder was obtained by a chemical deposition method using the NANOHIM hardware with a software complex. The setting of the experiment parameters, the control of all the devices, and the recording of the results were automated.During the chemical process and the nickel hydroxide sample preparation ,29, the The deposition was carried out in the reactor by the dosed supply of salt solutions and a precipitator with continuous stirring. The deposition temperature was maintained by the thermostat and the acidity was controlled with a pH meter. The obtained deposits were washed with distilled water and dried. Washing of the deposits was carried out by two methods: Centrifugation using a high-speed Hettich Rotanta 460  centrifuge (centrifugation was followed by dispersion in distilled water using a high-intensity ultrasonic treatment and subsequent centrifugation) and decantation. Additionally, ultrasonic treatment was carried out on one of the samples using a Hielscher UIP 1000hd  ultrasonic homogenizer to divide the aggregates during the deposition process. A Snol 58/350  drying oven was employed to dry the obtained precipitate of the nickel hydroxide. Solutions were pre-prepared with a given concentration, based on the required volume of the nano-sized product. The metallic nickel samples were obtained from the nickel hydroxides at various temperatures  and reduction times . A technological scheme of the nickel nanoparticles obtained is shown in The phase composition of powders before and after the reduction was studied by a Difrey-401 X-ray diffractometer using Cr kα radiation. The sizes of the coherent scattering regions were calculated for the (100) and (101) planes of the nickel hydroxide using the Scherrer equation. The microstructure and morphology of the obtained samples were analyzed using a TEM LEO 912 AB (Zeiss)  and a Tescan Vega 3 SEM. .3; and Ssp is the specific area, m2/kg.Specific surface area values for all the nickel hydroxide samples were obtained using the NOVA 1200e  analyzer by a low-temperature nitrogen adsorption method. The size of the aggregates from the experimental data under the assumption of their sphericity was calculated by Equation (1):sp is the specific area, m2/kg; d is the cylinder base diameter, m; h is the cylinder height, m; and ρ is the density, kg/m3.Verification of the specific surface area and dispersion characteristics obtained by electron microscopy was based on the cylindrical shape of the particles and was calculated by the following ratio (2):The number of nickel hydroxide plates (N) was estimated by Equation (3):The IR spectra were obtained by an Attenuated Total Reflectance (ATR) method using a Thermo Nicolet 380  spectrometer with a Smart iTR attachment. Each spectrum was obtained by the averaging of 32 mirror passes. The comparison spectrum was initially collected for each sample.The chemical and electronic states of atoms in the samples were determined using a PHI5500 VersaProbe II X-ray  photoelectron spectrometer. Monochromatized Al Kα radiation (hν = 1486.6 eV) at a 50 W power was used as the excitation source. The binding energy of the O1s photoelectron line was determined from the high-resolution spectra taken at an analyzer transmittance of 23.5 eV and a data collection density of 0.2 eV/step. The spectra were approximated by a nonlinear least-squares method using the Gauss‐Lorentz function. The binding energy scale was calibrated by the C1s spectrum of adsorbed hydrocarbons at 285.0 eV. The binding energies determination error was ±0.3 eV.2 phase (α-modification of the nickel hydroxide (α-Ni(OH)2·xH2O) with a hexagonal lattice. The X-ray diffraction patterns of the samples are presented in Based on X-ray analysis, all nickel hydroxide samples were shown to consist of the Ni(OH)2 lattice structure being deformed by the presented molecules of interlayer water.The calculation results of the nickel hydroxide lattice periods are presented in −1 intrinsic to OH group stretching vibrations in the interlayer water molecules [−1 correspond to the deformation vibrations of the water molecule hydroxyl groups.The presence of water molecules in the nickel hydroxide samples was confirmed by the results of IR and Raman spectroscopy see . A wide olecules  and the The microstructure of the nickel hydroxide is shown in Knowing the diameter of the aggregate, one can calculate its volume and number of nickel hydroxide plates (N) using Equation (3). The average particle diameters and the specific surface area for all of the nickel hydroxide samples were determined and are presented in The calculated data presented in Based on the obtained values of the dimensional characteristics, it was possible to estimate how many particles were in an average aggregate in each sample of the nickel hydroxide. For simplicity, we assumed that the units were cylindrical . In thisThe coherent scattering region (CSR) was determined in the direction perpendicular to the reflection planes. If the crystal is oriented as shown in Z-axis of the hexagonal lattice.The CSR sizes for all of the nickel hydroxide samples are presented in 2 hydroxide. In the form of the spectrum, there were no obvious twists or influxes for objective approximation, which indicated the absence of oxygen in the energy state corresponding to NiO molecules. Based on the fact that even individual molecules of nickel oxide were not detected, the process of hydrogen reduction of the α-modification of the nickel hydroxide proceeded without the formation of a nickel oxide phase.The presence of the NiO oxide in the samples could be detected by X-ray photoelectron spectroscopy by the peak in the O1s spectrum in the region of 532.6 eV . In the The TEM images of the samples after partial reduction a,b showe20;9;d;280;15). At the same time, the nickel nanoparticles retained the shape of a cube 2 and Ni average sizes, an estimation of the number of nickel hydroxide plates in one nickel particle was made. The calculation results are presented in After measurement of the Ni(OH)Therefore, one nickel particle with a 28 nm cube edge is formed from about 150 nickel hydroxide plates. According to the obtained results, the pattern of nickel nanopowder formation is shown in The growth of the nickel phase occurs outside, rather than inside, of the nickel hydroxide aggregate. The morphologies of the source material and the reduced product are completely different. The obtained results allow us to conclude that the formation of nickel nanoparticles from their hydroxide does not follow the “shrinking core” mechanism.Z-axis. Based on the obtained data, an estimated calculation of the number of plates forming individual aggregates was carried out. The calculation showed that their content varied from 28 to 3 × 105 plates in one aggregate.Regardless of the deposition and washing conditions, alpha modification of the nickel hydroxide with a hexagonal lattice was observed. The obtained hydroxide was an aggregate consisting of thin plates successively stacked on top of each other. The aggregate had a cylindrical shape of about a 1 nm height, with a base along the (001) plane and a height along the Various washing conditions lead to the formation of hydroxide with various dispersions. Decantation reduced the size of the aggregates and centrifugation reduced dispersion, evening out the effect of grinding by an ultrasonic treatment during the deposition process.Low-temperature reduction allowed us to obtain unreduced samples containing phases of both metallic nickel and nickel hydroxide. At the same time, the nickel oxide phase was not detected by X-ray analysis. The absence of the NiO phase was confirmed by photoelectron spectroscopy.The TEM studies of the two-phase samples, the metallic nickel nanopowder, and the dehydrated hydroxide (NiO), along with theoretical calculations, allowed us to make assumptions on the formation pattern of metallic nickel from its hydroxide during hydrogen reduction.