Patent Application
20240246882
The present invention relates to the controlled release fertilizers, particularly to a glass fertilizer which is phosphate-based and comprises the other oxides.
Plants need particular nutrient elements during their development process. C, H, and O, which constitute a large portion of them, are supplied from the air and water. Macro nutrient elements such as N, P, K, Mg, Ca, S, and micro nutrient elements such as B, Mo, Cu, Zn, Mn, Fe, Cl are taken from the soil. The fertilizers are widely used in order to increase the yield by supplementing these macro and micro nutrient elements required by the plant to the soil. The controlled release fertilizers (CRF) have also started to take place in the fertilizer sector with the aim of making an efficient agricultural production. The controlled release fertilizer term refers to a fertilizer that releases the nutrient elements in its structure into a medium over a long period of time. Since the controlled release fertilizers show controlled release, the amount of nutrient elements lost by washing from the soil in their use is significantly reduced. This provides a direct increase in the nutrient element uptake of the plants.
Glass has become a very popular material in the technology of controlled release fertilizer. Glass, which has no harmful effects on the environment, can contain many nutrient elements in its structure and as a result of its dissolution behavior in the soil medium, it contributes to plant nutrition by releasing the nutrients in its structure in a controlled manner. However, the chemical stability of glasses can be changed by the differences in its composition and glass fertilizers can be synthesized in accordance with the development processes and the needs of different plant species in terms of both content and dissolution.
The glass types studied in the literature are divided into two as silica-based and phosphate-based glasses. Although phosphate is a very good glass network former, the chemical stability thereof is very low when used alone. However, the chemical stability of phosphate glasses can be changed in a wide range by adding different components to the structure and by changing the ratios of the components. There are publications on phosphate glasses, which have a high potential for controlled release glass fertilizers due to their modifiable chemical stability.
U.S. Pat. No. 6,488,735 discloses a fertilizer component having a glass matrix containing, along with the network former oxides, a phosphorus pentoxide completely or partially instead of silica, modifier oxides of the glass matrix, as well as potassium oxide completely or partially instead of sodium oxide and containing one or more trace elements.
The primary objective of the present invention is to provide a controlled release fertilizer containing a phosphate-based glass composition, the release period of which can be adjusted widely depending on the type of the plant to be fertilized.
The present invention is a controlled release glass fertilizer composition comprising at least one macro element selected from the group comprising 28-50P2O5, 36>CaO and also 25>SiO2, 0.1-10Al2O3, 20>Na2O, 20>K2O as a mole percent, preferably an oxide selected from the group comprising SO3, MgO, and preferably a microelement selected from the group comprising Mn, Cu, B, Mo, Zn, Fe and having a glass transition temperature adjusted above 230° C. In a possible embodiment, the glass transition temperature is above 300° C. The samples of the P2O5— CaO—Na2O—K2O, P2O5— CaO—Al2O3— Na2O—K2O, P2O5— CaO—SiO2— Al2O3— Na2O—K2O systems were produced by using the conventional melting casting method in the varying ratios of Na2O/Na2O+K2O, Al2O3/P2O5 and SiO2/Na2O+K2O in the composition, respectively.
In a preferred embodiment, Na2O and K2O were selected from the group together as a macro element. In this case, it was determined that the dissolution rate was positively affected by the effect of mixed alkali.
In a possible configuration, it is possible to add nitrogen or the oxide thereof to the group as a macro element.
P2O5—CaO—Na2O—K2O
In a preferred embodiment, the macro elements are composed of P2O5, CaO, Na2O, K2O. Further, it comprises preferably SO3, MgO, SiO2 ve Al2O3 as oxides. Preferably, the components that form the glass composition are selected as 28-50P2O5— 10-35CaO—10-20Na2O (particularly 13-17)-10-30K2O in a mole ratio. In the P2O5— CaO—Na2O—K2O system, it was observed that nonlinear changes occurred in the Tg values of the samples with an increasing ratio of Na2O/K2O+Na2O and in the peak intensities and bandwidths of the PO3−2 group of the Q1 structural unit and the PO2− group of the Q2 structural unit; and it was determined that the mixed alkali effect caused this situation. Preferably, the density was adjusted to 2.54 g/cm3 for the mole percent ratio of 50P2O52OCaO15K2O15Na2O according to the ratio of Na2O/Na2O+K2O in the composition. As a result of the weight loss examinations of the samples of the P2O5— CaO—Na2O—K2O system, it was determined that the sample of 50P2O52OCaO15K2O15Na2O showed the slowest dissolution behavior. It is known that the dissolution mechanism in glasses is based on the exchange of alkali ions in the glass structure with hydrogen ions in the liquid medium and that the dissolution rate is controlled by the rate of ion migration in the hydrated glass layer and hydrolysis is also involved. Accordingly, it was determined that the slow dissolution behavior of the sample of 50P2O52OCaO15K2O15Na2O was caused by the low ionic migration rate due to the mixed alkali components therein.
In the preferred embodiment, the wave number of the FTIR spectrum comprises a reflectance peak between 520-540, 865-880, 1080-1090, 1260-1340 cm−1.
In a preferred embodiment, a pH change in the citric acid solution of 2% is adjusted less than 0.75, preferably less than 0.5 for over 600 hours.
P2O5—CaO—Al2O3—Na2O—K2O
In the P2O5— CaO—Al2O3— Na2O—K2O system, it was determined that along with an increasing ratio of Al2O3, an increase occurred in Tg values and the Q1 structural unit became more dominant in the structure. It was determined that this is a result of A13'0 ion with a high field intensity increasing the cross-links in the structure.
In the P2O5— CaO—Al2O3— Na2O—K2O system, it was determined that the chemical stability of the glass was improved significantly as a result of the addition of Al2O3 to the structure and the increase in the cross-links between the phosphate chains in the network structure, but that the dissolution rate accelerated in an acidic medium with a higher ratio of Al2O3.
On the other hand, in a preferred embodiment, the macro elements are formed from P2O5, CaO, Al2O3, Na2O, K2O. Preferably, the mole ratio of Al2O3 is chosen between 3-7. SiO2 is preferably chosen between 5-15 mole ratios.
In a preferred embodiment of the invention, according to the ratio of Al2O3/P2O5 in the composition, the density was adjusted to 2.63 g/cm3 for the mole percent ratio of 45P2O520CaO5Al2O315Na2O15K2O.
Preferably, the wave number of the FTIR spectrum comprises a reflectance peak between 530-550, 880-905, 1100-1120, 1180-1270 cm−1.
Preferably, the pH change in the citric acid solution of 2% is adjusted less than 0.75 for over 600 hours. It was determined that the chemical resistance increased in the acidic solvent medium with Al2O3 added to the structure, but that decreased in the neutral medium.
P2O5—CaO—SiO2—Al2O3—Na2O—K2O
In a preferred embodiment of the invention, the macro elements are composed of P2O5, CaO, SiO2, Al2O3, Na2O and K2O.
Preferably, the density was adjusted to 2.60 g/cm3 for the mole percent ratio of 45P2O520CaO5SiO25Al2O312.5Na2O12.5K2O according to the ratio of SiO2/Na2O+K2O in the composition. By evaluating the physical, thermal, structural analysis results and dissolution behavior of all synthesized samples, it was determined that the sample of 45P2O520CaO5SiO25Al2O312.5Na2O12.5K2O is the most suitable glass for the development of tomato plants. It was determined that an increase occurred in the Tg value with SiO2 added to the structure, while Si—O—P bonds were formed in the structure. The microelement is used as the glass fertilizer in the pot experiments performed with the tomato plant with additives (MnO2, Fe2O3, ZnO, B2O3, CuO, MoO3) and without additives. Preferably, the wave number of the FTIR spectrum comprises a reflectance peak between 490-535, 880-895, 1090-1100, 1260-1265 cm−1. Preferably, the pH change in the citric acid solution of 2% is adjusted less than 0.75 for over 600 hours.
P2O5—CaO—MgO—Na2O—K2O
The invention preferably comprises the P2O5— CaO—MgO—Na2O—K2O system. The sample of 50P2O520CaO7.5MgO7.5Na2O15K2O can be obtained as homogeneous glass with the assayed production parameters.
A preferred embodiment of the invention includes the use of a glass fertilizer composition in the production of tomato (Lycopersicon Esculentum), except for a sample of 50P2O520CaO30K2O suitable for any of the above embodiments. As a result of the pH monitoring carried out, it was determined that no sample significantly alter the pH of the acidic solvent medium and the pH values of the medium were in a pH range ideal for the development of tomato plants during their dissolution in neutral medium, except for the sample of 50P2O520CaO30K2O.
In this detailed description, the configurations of the invention and its preferred embodiments are described only for a better understanding of the subject and in a non-limiting sense.
Application areas of phosphate glasses remained restricted in the past due to their low chemical resistance properties. The poor chemical resistance of phosphate glasses is thought to be originated from the asymmetry of the PO4 tetrahedron which is the basic building block of phosphate glass. Nevertheless in recent years, phosphate glasses have become an intensively studied material for the controlled release fertilizers. The dissolution behavior of phosphate glasses depends on the glass composition, the pH value of the solvent medium, the temperature, the thermal history of the glass, and the glass surface area.
In the studies in the literature, it has been stated that three types of reactions may play a role during the dissolution of phosphate glass in a liquid medium. These are the acid-base, hydrolysis and hydration reactions. The acid-base reaction is responsible for the disruption of the ionic interaction between the chains in the network structure, which is highly pH dependent. During the hydration reaction, the highly mobile cations (such as Na+) in the glass structure are replaced with the H+ ions in the water structure. As a result of this ion exchange, a hydration layer is formed at the glass-water interface. At this stage, P—O—P bonds in the hydration layer are broken by the effect of the water molecules and the hydrogen ions, and the hydrolysis reaction takes place. This results in the deterioration of the network structure of the glass and the passage of the phosphate chains of different lengths into solution. This step highly depends on the ambient pH, as it will accelerate with the increase of the H+ ion concentration in the solution. In an acidic medium, the protons increase the dissociation of the P—O-M bonds. Therefore, as compared to a neutral medium, an acidic medium will lead to a higher rate of hydration reaction and dissolution.
In the disclosed embodiments of the invention, the samples of different phosphate-based glass compositions were produced by the conventional melting casting method, the glass samples obtained were examined physically, thermally and structurally, the dissolution behavior of the glass samples in the different solvent media was monitored and the effect of the composition change on the chemical stability of the glass was determined. In the light of the data obtained, the glass fertilizer composition, which is thought to be the most suitable for use in the development of the tomato plant, was determined and the microelements required by the plant were also added to this composition. The samples of glass compositions with and without the microelement additives were used to grow the tomato plants, and the effect of the obtained glass fertilizer on plant growth was investigated.
During the production of glass samples, P2O5 (99.0%, Sigma Aldrich), CaCO3 (99%, Merck-Suprapur), Na2CO3 (99.5%, Alfa Aesar), K2CO3 (98.5%, Sigma Aldrich), MgO (98%, Sigma Aldrich), Al2O3 (99.9%, Alfa Aesar), SiO2 (99.8%, Sigma Aldrich), ZnO (99%, Merck-Supelco), CuO (99%, Alfa Aesar), Fe2O3 (99.5%, Alfa Aesar), MoO3 (99.95%, Alfa Aesar), MnO2 (95%, Honeywell-Riedel de Haen) and H3BO3 (99.9%, Zag Kimya) powders of high purity were used as a starting material. The carbonate compounds of the alkaline earth and the alkalis used as the starting materials turned into the oxides as a calcined form during melting. The properties of the oxidized compounds involved in the sample production are given in Table 1.
During the sample production, the calculations were made based on the molar weights of the raw materials used. The denomination of the samples was made by writing the initials of the components and the theoretical mole percentages side by side. The sample codes are given in Table 2 and Table 3 along with their compositions.
For the purpose of producing the glass samples, according to the compositions determined, the raw materials were weighed on Precisa™ 10−4 precision scales and a homogeneous powder mixture was obtained by mixing them in an agate mortar. The prepared powder mixtures were melted in the Protherm PLF 160/9 furnace, and due to the change in the composition, a 30-minute preheat step at 700° C. was added to the production process for some samples. The melting process was carried out for 20 and 60 minutes for samples with different compositions, and the melting temperature varied between 1000° C.-1300° C. After melting, the samples were poured into a preheated stainless steel mold and then subjected to stress relief annealing for 3 hours at temperatures ranging from 250° C.-380° C. in a Protherm PLF 120/5 furnace. After annealing, the samples were cooled down to the room temperature in a controlled manner in the furnace. Before the characterization stage, one surface of the obtained samples was sanded with 320, 800, 1200 and 2500 grit sandpapers, respectively, and polished with diamond paste (Struers—diaduo-2). The chemical analysis of the samples was performed using an X-ray fluorescence spectrometry (XRF) method for the selected samples in order to detect whether there was any deviation in the composition during manufacture. The prepared powder samples were mixed with cellulose at a ratio of ⅓ and then pressed and analyzed with the Rigaku—ZSX Primus II model XRF device. In order to interpret the changes in the glass structure depending on the composition of the samples obtained, the values of density, ρ, molar volume, VM, oxygen molar volume, VO, oxygen packing density, OPD, were calculated.
The densities of the glass samples were determined by 3 repetitive measurements using the Archimedes method on a precision scale with a sensitivity of 10−4, and ethanol was used as a dipping liquid. The densities of the glass samples were calculated according to Equation 1.
In the equation, ρ is the density of the glass, ρEthanol is the density of the ethanol used as the dipping liquid, WAir is the weight of the glass in the air, and WEthanol is the weight of the glass in ethanol.
The molar volumes, VM, of the glass samples were calculated according to Equation 2.
According to the equation, Xi is the mole fraction of the components, Mi is the molecular weight of the components, and ρ is the density of the sample.
The oxygen molar volumes, VO, of the glass samples were calculated according to Equation 3.
According to the equation, Xi is the mole fraction of the components, Mi is the molecular weight of the components, ρ is the density of the sample, and ni is the number of oxygen atoms in each oxide.
The oxygen packing densities, OPD, of the glass samples were calculated according to Equation 4
In the equation, C is the number of oxygen atoms for each composition, p is the density, and M is the molecular weight.
The thermal properties of the obtained glass samples were determined by the differential thermal analysis (DTA) method.
FTIR analysis of the sample of P45C20S5A5N12.5K12.5-M was performed on a powder sample using Bruker Vertex 70 instrument with Pt ATR in the wave number range of 400-4000 cm−1. In order to examine the dissolution behavior of the synthesized samples, the time-dependent weight loss was monitored in two different media, distilled water and 2% citric acid solution. While the distilled water used as a solvent represents a neutral medium, the 2% citric acid solution simulates the pH value of the medium where the nutrient elements are taken from the root region into the plant. The samples obtained for the weight loss studies were placed in both solvent media based on the ratio of the sample weight/solvent weight=0.1. The weights of the samples, which were left in the solvent medium, were monitored at 0.5, 1 and 2 hours on the first day, then at 24-hour intervals for a week and once a week in the following period. The dissolution rates of the glass samples were calculated using Equation 5.
According to the equation, DR is the dissolution rate, Wi is the first weight of the sample, Ws is the last weight of the sample, A is the initial surface area of the sample, and t is the time during which it remains in the solution. During the dissolution of the samples, pH monitoring of the solvent medium was performed with a WTW Inolab pH/cond 720 model pH meter with an accuracy of 0.005. The pH changes in the solutions were monitored by taking measurements at certain intervals, at 24-hour intervals in the first week of dissolution, and once a week thereafter. In order to determine the amount of ions released from the glass sample over time during dissolution, two separate sets of experiments were created using different solvents. For two solvent media for which 2% citric acid solution and distilled water are used, at the end of the weeks 1, 2, 3 and 4, the amounts of ions that passed into the solution were determined by inductively coupled plasma—optical emission spectrometry (ICP-OES). Before the analysis performed using a Perkin Elmer Avio 200 model ICP-OES device, calibration was performed at 4 points using the standard solutions, and while a 100-fold dilution was applied for 2% citric acid solution before each measurement, no dilution was performed for distilled water. Pot experiments were carried out to examine the effect of the selected glass fertilizer composition on the growth of tomato plants. 4 different pot experiments, including the control sets, were set up. To this end, 4 cherry tomato seedlings were planted in pots of 3 liters. 1. The pot does not contain fertilizer, 2. The pot contains a glass fertilizer of the determined main composition, 3. The pot contains a glass fertilizer with a microelement additive, and 4. The pot contains a chemical fertilizer (NPK). The glass fertilizers with and without a microelement additive in the pot experiments were ground in a grain size range of 0.25-0.50 mm and mixed homogeneously with the soil, and the amount of the glass fertilizer was calculated according to the amount of the elements that the tomato plant absorbs during its development and to the results of the dissolution test of the determined glass fertilizer composition. However, each pot is illuminated by full spectrum led lamps used for plant growing, and the temperature and the humidity of the environment were monitored with a TT-Technic HTC-I clock moisture meter and thermometer. During plant development, the height of the seedlings was measured in weekly periods and the change in their height was recorded, and the fruit number, the weight, the average leaf size and the average stem thickness were determined.
In this section, the results of physical, thermal, structural analysis and the dissolution behavior of all glass samples produced in varying compositions in the P2O5— CaO—Na2O—K2O, P2O5—CaO—Al2O3— Na2O—K2O, P2O5— CaO—SiO2— Al2O3— Na2O—K2O systems are given in detail.
The sample of P50C20K30 containing 50% P2O5, 20% CaO and 30% K2O by mole was obtained as homogeneous, transparent and colorless at the end of the melting casting process. In order to determine the physical properties of the sample of P50C20K30, the density value was measured and determined to be 2.481 g/cm3. By using the density value obtained, the molar volume, the oxygen molar volume and the oxygen packing density of the sample were calculated and given in Table 4 together with the ratio of O/P.
The thermal characterization of the sample of P50C20K30 was carried out by a DTA analysis, and the analysis result is given in
The result of the FTIR analysis performed for the structural characterization of the sample of P50C20K30 is given in
In order to determine the dissolution behavior of the sample of P50C20K30, the weight loss tracking carried out in two different media being distilled water and 2% citric acid solution, are given in
During the dissolution of the sample of P50C20K30, the pH changes in the solvents were monitored and the results obtained are given in
The change in weight % of the sample of P50C20K30 in the distilled water and 2% citric acid solution by the weight change and the pH changes in the solvents are given in
In order to examine the physical properties of the sample of P50C20N15K15, the density thereof was measured, and the density value was determined to be 2.539 g/cm3. By using the measured density value, the values of molar volume, oxygen molar volume, oxygen packing density of the sample were calculated and given in Table 6 together with the determined O/P value.
The result of the DTA analysis performed for the thermal characterization of the sample of P50C20N15K15 is given in
The result of the FTIR analysis performed for the structural characterization of the sample of P50C20N15K15 is given in
During the dissolution of the sample of P50C20N15K15 in two different media, the pH of the solvents were followed, and the pH changes in citric acid on the left and distilled water on the right are given in
The change in weight % of the sample of P50C20N15K15 in distilled water and 2% citric acid solution and the pH changes in the solvents are given in
As a result of the applied production conditions, the sample of P50C20N30 was obtained as homogeneous, transparent and colorless. In order to determine the physical properties of the sample of P50C20N30, the density thereof was measured, and the values of molar volume, oxygen molar volume and oxygen packing density were calculated. The obtained results are given in Table 8 along with the calculated O/P value of the sample.
The result of the DTA analysis performed for the thermal characterization of the sample of P50C20N30 is given in
The result of the FTIR analysis performed for the structural characterization of the sample of P50C20N30 is given in
The results of the weight loss examinations carried out in two different media in order to observe the dissolution behavior of the sample of P50C20N30 are given in
During the dissolution of the sample of P50C20N30 in two different solvent media, the pH changes in the solvents were monitored and the results obtained are given in
The change in weight % of the sample of P50C20N30 in the distilled water and 2% citric acid solution and the pH changes in the solvents are given in
During the melting process carried out during the production of the sample of P50C20M7.5N7.5K15, it was observed that the sample overflowed and many different methods were tested for the production of the sample. According to the determined production method, there was an increase to 700° C. at 10° C./min, a pre-heating process was applied at this temperature for 30 minutes, and the melting was carried out for 60 minutes again with an increase to 1275° C. at 10° C./min. XRF analysis of the sample obtained with the aforementioned production method was performed and the sample was compared to the determined glass blend composition. According to the results given in Table 10, it was determined that there was no significant deviation from the blend composition and that the applied production method was suitable for the production of the sample of P50C20M7.5N7.5K15.
Two different methods were tested for the production of the sample of P50C20M15K15. In the first production method, the prepared powder mixture was melted at 1275° C. for 30 minutes and poured into a preheated, stainless steel mold and subjected to stress relieving annealing at 350° C. for 3 hours. In the second production method, it was melted at 1275° C. for 1 hour and the obtained sample was ground and melted again at 1300° C. for 1 hour. After casting, the sample was subjected to the stress relief annealing at 350° C. for 3 hours. As a result of the applied production methods, the sample of P50C20M15K15 could not be obtained homogeneously. Since the sample could not be obtained homogeneously, a detailed study was not carried out on the change in the physical, thermal, structural properties and the dissolution behavior of the glasses of the P2O5— CaO—MgO—Na2O—K2O system.
The sample of P50C20A5N15K15 containing 45% P2O5, 20% CaO, 5% Al2O3, 15% Na2O and 15% K2O by mole was obtained as homogeneous, transparent and colorless as a result of the production method applied.
In order to examine the physical properties of the sample of P45C20A5N15K15, the density thereof was measured and the values of molar volume, oxygen molar volume and oxygen packing density were calculated. The obtained results are given in Table 11 along with the calculated O/P value of the sample.
The result of the DTA analysis performed in order to determine the thermal properties of the sample is given in
The result of the FTIR analysis performed for the structural characterization of the sample of P45C20A5N15K15 is given in
The result of the weight loss examinations carried out in two different solvent media in order to examine the dissolution behavior of the sample of P45C20A5N15K15 is given in
During the dissolution of the sample took place in two different solvent media, the pH values of the solvents were monitored, and the results are given in
The change in weight % of the sample of P45C20A5N15K15 in the distilled water and 2% citric acid solution and the pH changes in the solvents are given in
The sample of P40C20AlON15K15 was obtained as homogeneous, transparent and colorless under the applied production conditions.
In order to examine the physical properties of the sample, the density measurement was carried out, and the values of molar volume, oxygen molar volume and oxygen packing density were calculated. The results obtained are given in Table 12.
The result of the DTA analysis performed in order to determine the thermal properties of the sample of P40C20AlON15K15 is given in
In order to examine the dissolution behavior of the sample of P40C20AlON15K15, the weight loss tracking was performed in two different solvent media, and the results are given in
During the dissolution of the sample took place in two different solvent media, the pH values of the solvents were monitored and the results are given in
The change in weight % of the sample of P40C20AlON15K15 in the distilled water and 2% citric acid solution and the pH changes in the solvents are given in
The sample of P45C20S5A5N12.5K12.5 was obtained as homogeneous, transparent and colorless under the applied production conditions.
XRF analysis of the sample obtained was performed, and the sample was compared to the determined glass blend composition. According to the results given in Table 13, it was determined that the amount of P2O5 obtained as a result of the analysis was lower than the amount in the blend composition depending on the melting conditions, while CaO and K2O amounts were higher than those in the composition due to the normalization of the analysis results according to the new P2O5 amount obtained.
In order to examine the physical properties of the sample, the density thereof was measured and the values of molar volume, oxygen molar volume and oxygen packing density were calculated. The results obtained are given in Table 14.
The result of the DTA analysis performed in order to examine the thermal properties of the sample of P45C20S5A5N12.5K12.5 is given in
The result of the FTIR analysis performed for the structural characterization of the sample of P45C20S5A5N12.5K12.5 is given in
In order to examine the dissolution behavior of the sample, the weight loss tracking was performed in two different solvent media and the results are given in
During the dissolution of the sample took place in two different solvent media, the pH values of the solvents were monitored and the results are given in
The change weight % of the sample of P45C20S5A5N12.5K12.5 in the distilled water and 2% citric acid solution and the pH changes in the solvents are given in
The amounts of P, Ca, Si, Al, Na and K which passed into the solvent medium depending on time during the dissolution of the sample of P45C20S5A5N12.5K12.5 in 2% citric acid solution and distilled water were determined by ICP-OES, and the results are shown in
When the results were examined, it was determined that the amounts of P, Ca, Si, Al, Na and K increased over time during the dissolution of the sample of P45C20S5A5N12.5K12.5 in distilled water. During the dissolution in 2% citric acid solution, it was observed that the amounts of P, Ca, Si, Al, Na and K, which passed into the solvent during the first 3 weeks, increased over time, but when the results of the 3rd and 4th weeks were compared, it was observed that for each element, there was a passage into solution in proximate proportions. It was determined that this case may be due to the slowing down of the dissolution depending on the increase in the solvent concentration.
The sample of P45C20S5A5N12.5K12.5-M was obtained as homogeneous, transparent and green under the applied production conditions.
In order to examine the physical properties of the sample, the density measurement was carried out, and the values of molar volume, oxygen molar volume and oxygen packing density were calculated. The results obtained are given in Table 15.
The spectrum obtained as the result of the FTIR analysis performed for the structural characterization of the sample of P45C20S5A5N12.5K12.5-M is given in
The spectrum obtained as the result of the DTA analysis performed in order to determine the thermal properties of the sample of P45C20S5A5N12.5K12.5-M is given in
The dissolution behavior of the sample of P45C20S5A5N12.5K12.5-M with a microelement additive was not investigated and this sample was used directly in the pot experiments.
The results of physical, thermal, structural analysis and the dissolution behavior of the glass samples of the P2O5— CaO—Na2O—K2O, P2O5— CaO—Al2O3— Na2O—K2O, P2O5— CaO—SiO2— Al2O3— Na2O—K2O systems are evaluated respectively according to the varying Na2O/Na2O+K2O, Al2O3/P2O5 and SiO2/Na2O+K2O composition, and the effect of the glasses with and without additives, which were determined to be suitable for the development of a tomato plant, on the development of tomato plant was interpreted.
The values of densities, theoretical densities, molar volume, oxygen molar volume and oxygen packing density of the glass samples obtained in the P2O5— CaO—Na2O—K2O system, which were measured for the purpose of examining the physical properties, are given in Table 16, and the changes in the values of density, molar volume, oxygen molar volume and oxygen packing density according to the varying ratio of Na2O/Na2O+K2O in the composition are shown in
When the results are examined, it is seen that the theoretical density decreases as the ratio of K2O in the structure decreases and the ratio of Na2O increases. This is caused by the fact that the density of K2O (2.35 g/cm3) is slightly higher than that of Na2O (2.27 g/cm3). However, when the experimentally obtained density results were examined, it was determined that the density increased as the ratio of K2O in the structure decreases. This difference between the theoretical and measured densities can be understood by the difference between the radii, densities and values of electronegativity of the alkali ions. The radius of the K+ ion (1.38 Å) is larger (1.02 Å) than the Na+ ion, and accordingly the K+ ion density (0.862 g/cm3) is lower than the Na+ ion density (0.971 g/cm3). In addition, the electronegativity value of the K+ ion (0.82) is lower than the Na+ ion (0.93), which causes a looser network structure. Therefore, as the ratio K2O in the composition decreases, a decrease in the molar volume values occurs.
It was determined that the oxygen molar volume values decreased with the decreasing ratio of K2O/Na2O+K2O in the structure. This is caused by the tighter packing of the structure as a result of the replacement of the K+ ion with lower field strength (0.13) by the Na+ (0.17) ion with higher field strength.
On the other hand, the oxygen packing densities of the glasses increased with the decrease of the ratio of K2O/Na2O+K2O, in contrast to the VO values. It was determined that an increase in OPD values resulted from the formation of a more tightly packed structure by the replacement of the K+ ion by the Na+ ion with higher field strength, considering that the total number of oxygen possessed by each sample composition is the same.
The thermal stability values calculated with the values of glass transition, crystallization onset and peak temperature determined to be a result of the thermal analysis of the glass samples of the P2O5— CaO—Na2O—K2O system are given in Table 17.
When the results are examined, although there is not a significant difference between the Tg values for the samples of P50C20K30 and P50C20N30, it is seen that the sample containing 30% Na2O by mol has a higher Tg value than the sample containing 30% K2O. This is caused by the looser structure of the sample of P50C20K30, as the K+ ion has a larger ionic radius and a lower field strength than the Na+ ion. Theoretically, while the ratio of K2O in the structure increases and the ratio of Na2O decreases, the amount of NBO will increase as the P—O—P bonds are broken, and this will cause a decrease in Tg values. However, when the results obtained were examined, no linear change was observed in the Tg values with the increase in the amount of Na2O in the composition, and the lowest Tg value was obtained for the sample containing 15% Na2O by mole. This non-linear behavior observed at the transition temperatures of the samples with the increasing ratio of Na2O in the structure is a result of the mixed alkali effect (MAE). The mixed alkali effect represents a behavior of change in the properties (ionic diffusion, ionic conductivity, dielectric relaxation, glass transition temperature, viscosity etc.) of the glass depending on the structure and ion movement, as a result of the gradual replacement of an alkali ion in the structure by another alkali ion in multi-component glass systems, and this change does not show linearity with the change in the composition. The negative deviation from linearity observed at the glass transition temperatures, which occurs with MAE, is explained by a defect model proposed by LaCourse in the literature. According to this model, in the mixed alkali-containing glasses, M-O-M (M: network former cation) bonds are broken as a result of the reorganization of the ionic regions together with the jump of ions to foreign regions. This situation shifts Tg values towards lower temperatures by increasing the breakdown of the network structure and the formation of structural errors.
The thermal stability values of the glass samples varied between 71 and 77° C. and showed an increase with the increasing ratio of Na2O.
FTIR spectra of the samples of glass in the range of 400-1400 cm−1 are given in
The properties of the vibrations observed in the spectra were determined by reviewing the literature data, and when the spectra obtained were examined, 3 strong peaks were observed for each sample. The peak around 530 cm−1 represents O═P—O or P—O—P bonds, while the peaks observed around˜880 cm−1 and ˜1280 cm−1 represent the P—O—P bonds and PO2− group of the Q2 structural unit, respectively. This shows that all samples obtained in the P2O5—CaO—Na2O—K2O system have a structure dominated by the Q2 unit, and this result is also consistent with the O/P values calculated for the samples.
The peaks observed between the wave numbers of 640 cm−1-780 cm−1 are caused by the vibrations of P—O—P bonds. While there were 3 peaks in this region for the sample containing 30% K2O by mole, the peak at wave number of 648 cm−1 disappeared with the addition of Na2O to the structure. In addition, with the increasing ratio of Na2O, it was determined that the shoulder observed at the wave number of ˜1012 cm−1, which represents the P—O—P bond, was shifted towards the wave number of ˜983 cm−1. It was determined that this situation was caused by the increase in the P—O—P bond.
The peaks observed at 1083 cm−1 and 1265 cm−1 are caused by the vibrations of the PO3−2 group of the Q1 structural unit and the PO2− group of the Q2 structural unit, respectively, and the intensities of the peaks show a nonlinear change with the increasing ratio of Na2O. However, it was observed that the peak observed at 1174 cm−1 and caused by the symmetrical vibration of the PO2− group of the Q2 structural unit was shifted to lower wavelengths with the increasing ratio of Na2O. Furthermore, in the spectrum of the sample of P50C20K30, it is seen that the peak caused by the vibration of the P═O bond of the Q3 structural unit observed at 1336 cm−1 disappears with the increasing ratio of Na2O in the structure. In the literature, the fact that Q2 and Q1 structural units can be observed and Q3 units cannot be observed in the samples with the varying ratios of CaO/Na2O in the constant P2O5 composition is explained by the effect of the melting process on the glass structure. It was indicated that this difference in the glass structure may have resulted in the reduction of cross-links in the glass structure as a result of phosphate losses during melting, and this may have resulted in the lack of the Q3 unit in the structure.
The bandwidth is related to the specific variety of bond angles, bond lengths, and coordination types of charge-balancing cations. When the FTIR analyzes of the glass samples of the P2O5—CaO—Na2O—K2O system were evaluated in general, it was determined that there were changes in the intensities and positions of the peaks depending on the varying composition, and that with the increasing ratio Na2O/Na2O+K2O, a non-linear change occurred in the peak intensities and the band widths of the PO3−2 group of the Q1 structural unit and the PO2− group of the Q2 structural unit. This nonlinear variation observed for the non-bonding oxygen is a result of MAE. Na+ ion tends to exist in the NBO regions by creating regions of certain diameter with a certain coordination with the non-bonding oxygen (NBO) within the structure. On the other hand, K+ ions have a different NBO coordination and create larger regions. At low temperatures, although most K+ ions will be located in the potassium regions and most Na+ ions will be located in the sodium regions, some of the cations in the structure will be located in the other cation region. This situation is caused by the mixed alkaline effect.
The time-dependent weight loss behavior of the glass samples obtained in the P2O5— CaO—Na2O—K2O system in 2% citric acid solution and distilled water are given in
When the data obtained were examined, it was seen that the fastest dissolution was occurred for the sample containing 30% K2O by mole in both media, that the dissolution rate was the lowest observed with the addition of 15% Na2O to the composition, and that a slight increase occurred in the dissolution rate once Na2O completely replaced K2O.
The rapid dissolution of the sample of P50C20K30 in both media is caused by the fact that the K+ ion with low field strength and large ion radius lead to a looser glass structure. On the other hand, it is observed that the dissolution of the sample of P50C20N30 is slower than the sample containing 30% K2O by mole. This is a result of Na+, which has a smaller ionic radius and higher electronegativity, forming a tighter network.
It was determined that the slowest dissolution was observed for the sample of P50C20N15K15, and that there was a negative deviation from linearity in the change of the chemical resistance property of the glass with the composition in this sample. This situation is thought to be a result of mixed alkaline effect. In the literature, many models have been focused on to explain the mixed alkali effect. Maas et al. demonstrated a dynamic structure model by showing the formation of energy mismatch in the cation regions and the effect thereof on the ion transport. According to this model, a drastic decrease in the ion mobility of the glasses which contain mixed alkali occurs as a result of the effective inhibition of ion conduction pathways due to the region mismatch. The random ion distribution model, which is consistent with the dynamical structure model, similarly states that the ions retain their local regions relative to the glass which contains a single modifier, leading to a mismatch between different ion regions, thus reducing the number of regions available for the ion migration.
In accordance with the results obtained, it was determined that all samples showed a similar trend in both neutral and acidic media, and it was observed that the samples in 2% citric acid solution showed a faster dissolution behavior compared to distilled water. The rapid dissolution behavior of the samples in 2% citric acid solution with a low pH value is the result of the acceleration of the hydration reaction, which is one of the effective reactions in the dissolution mechanism of phosphate glasses, with the increase of H+ ion concentration.
The pH changes of the glass samples obtained in the P2O5— CaO—Na2O—K2O system during their dissolution in the 2% citric acid solution and distilled water media are given in
When the pH changes in the citric acid solution are examined, it was observed that the pH change occurred in a very limited range, and it was determined that the pH value of the solution increased in the first stages of the dissolution and did not change significantly in the following stages. The dissolution process starts and continues with the reaction of H2O, OH−, H+ (or H3O+) at the glass-solvent interface. Hydration and hydrolysis reactions play an active role in the dissolution of the glass samples. With the hydration reaction, the hydrogen ions in the solution replace the mobile ions in the network structure and form a hydrated layer at the glass-solvent interface. The P—O—P bonds are broken as a result of the breakdown of this hydrate layer formed by the hydrolysis reaction. During the dissolution in 2% citric acid solution, the H+ ions in the solution began to be depleted in accordance with the hydration reaction, and consequently, an increase in the pH values of the solutions was observed in the early stages of the dissolution. In the following stages of dissolution, the ratio of H+ ion consumed decreased considerably. It is known in the literature that reaching an increase in the concentration of the groups that pass from the glass structure to the solution, a level sufficient to form a buffer solution after a certain point can have a similar effect on the pH value. The fact that the pH values observed for all samples did not change in the following hours in
When the effects of the samples dissolved in distilled water on the pH value of the solution were examined, it was observed that the pH value of the sample of P50C20K30 suddenly decreased to the acidic region (˜3.0). This is the result of a rapid dissolution due to the loose network structure formed by K+ ion with a large ion radius. It is thought that this sudden decrease in pH value is due to the rapid increase in HPO4 and PO4−3 concentrations in the solution as a result of the rapid dissolution behavior. For the samples of P50C2ON15K15 and P50C20N30, which showed a slower dissolution behavior, an increase in the pH values was observed at the beginning of the dissolution as a result of the consumption of H+ ions in the solution in accordance with the hydration reaction. In the following stages, as a result of the hydrolysis reaction, the P—O—P bonds are broken and the P—OH− group is formed. The formed P—OH− group can be deprotonated depending on the pH of the solution. Therefore, with the hydrolysis reaction, the H+ ion concentration in the solution increases and the pH value decreases. At the following stages of the dissolution, the pH values for all samples remain at an almost constant value. It is thought that this situation arises from the fact that the solution acts as a buffer solution after a certain point with an increase in the ion concentration in the solution.
The measured values of densities, theoretical densities, molar volume, oxygen molar volume and oxygen packing density of the glass samples synthesized in the P2O5— CaO—Al2O3— Na2O—K2O system are given in Table 18 for the purpose of examining the physical properties. The change in density, molar volume, oxygen molar volume and oxygen packing density depending on the Al2O3/P2O5 contents of the samples is shown in
The measured densities of the obtained samples are compatible with the calculated theoretical densities of the glasses, and it is observed that the density values of the samples increase with the replacement of P2O5 in the structure at a constant alkaline earth and alkaline oxide concentration, by Al2O3, which has a higher density. However, a decrease in molar volume was observed with the increase of Al2O3 amount in the structure. This is due to the lower molar mass and the higher density of Al2O3 compared to P2O5.
When the oxygen molar volumes of the samples were examined, no significant change was observed in the values of the oxygen molar volume with the increasing amount of Al2O3. It was observed that the oxygen packing densities increased slightly with the increasing Al2O3 ratio, since Al+3 (0.84) ion with a high field strength formed cross-links in the structure and made the structure tighter. This situation is caused by the fact that the Al+3 ion creates a more tightly packed structure by increasing the cross-links in the structure.
The thermograms obtained as a result of the thermal analysis of the glass samples of the P2O5—CaO—Al2O3—Na2O—K2O system are given in
As a result of the DTA analysis, it was determined that the transition temperature increased from 376° C. to 446° C. with the increase of the ratio of Al2O3/P2O5. When the Al+3 ion having a high field strength enters the structure, it forms cross-links with the phosphate chains, and P—O—P bonds in the structure are replaced with stronger covalent P—O—Al bonds. This situation causes an increase in the glass transition temperature with an increasing ratio of Al2O3.
The FTIR spectra of the glass samples synthesized in P2O5—CaO—Al2O3—Na2O—K2O system are given in
When the obtained spectra were examined, it was determined that the peak around 533 cm−1 represented O═P—O or P—O—P bonds, and as a result of increasing the ratio of Al2O3 to 10% by mole, a new peak formation was observed at the wave number of ˜545 cm−1. This peak is caused by the vibration of the octahedral AlO6 group.
The peaks observed in the wave number range of 720-780 cm−1 are caused by the vibrations of the P—O—P bonds in the P2O62− group in the metaphosphate chains. For the sample containing 5% Al2O3 by mole, two weak peaks were observed in this region, as a result of the increase in the amount of Al2O3, the peak at the wave number of ˜710 cm−1 disappeared, while the peak at the wave number of ˜757 cm−1 was shifted to ˜744 cm−1. According to the literature, the peak observed at the wave number of ˜740 cm−1 is caused by the vibrations of the P—O—P bonds in the P2O74− pyrophosphate group. This change observed in the spectrum is the result of the depolymerization of the (P2O62−)∞ group, and the formation of the short phosphate groups such as P2O74− and PO43− results from a gradual breaking of the endless chains in the metaphosphate glass structure with the increase of the ratio of Al2O3/P2O5.
It was observed that the peak at the wave number of 883 cm−1, which was caused by the vibrations of the P—O—P chains of the Q2 structural group, was shifted to the wave number of 900 cm−1 with an increasing ratio of Al2O3. However, the shoulder which is observed at 980 cm−1 for the sample containing 5% Al2O3 by mole and which is observed due to the P—O—P bonds that form the wide annular structures of the Q2 structural unit, was shifted to the region (1041 cm−1) where the peaks caused by the vibrations of the PO3−2 group of the Q1 structural unit were observed, with the increase of the ratio of Al2O3/P2O5.
It was determined that the peak formed at the wave number of 1103 cm−1 and caused by the asymmetric stretching vibration of the PO3−2 group of the Q1 structural unit was shifted to a higher wavelength (1115 cm−1) with an increasing ratio of Al2O3, and it was detected that the intensity of the peak, which is present at 1184 cm−1 and caused by the symmetrical vibration of the PO2− group of the Q2 structural unit, increased with an increasing amount of Al2O3. However, it was observed that the peak, which is observed at the wave number of 1263 cm−1 and represents the PO2− group of the Q2 structural unit, disappeared with an increasing ratio of Al2O3/P2O5. It is thought that these changes observed in the obtained spectra may be a result of the replacement of P—O—Al bonds with P—O—P bonds, with Al2O3 replacing P2O5, and of the decrease in the phosphate chain lengths of the Al+3 ion with high field strength entering the structure at an increasing ratio of O/P.
The data obtained from the weight loss examinations of the glass samples synthesized in the P2O5—CaO—Al2O3—Na2O—K2O system in 2% citric acid solution and distilled water medium, are given in
When the results obtained are examined, as the H+ concentration is higher in the acidic solution, the hydration reaction takes place more effectively, and the dissolution occurs faster than in distilled water.
Theoretically, as a result of the increase of the ratio of Al2O3/P2O5, it is expected that the Al+3 ion will form strong cross-links between the phosphate chains and that there is an increase in the chemical resistance as smaller phosphate groups replace the longer phosphate chains, which are more sensitive to hydration, with an increasing ratio of O/P. However, when the experimental results were examined, the sample containing 10% Al2O3 by mole in 2% citric acid solution showed a faster dissolution behavior. In distilled water, while the sample containing 10% Al2O3 by mole showed a faster dissolution during the first month, the sample containing 5% Al2O3 by mole dissolved faster in the following stages. This situation, which is inconsistent with the theoretically expected results, can be explained by the AlOx groups in the structure. Al2O3 can be found in 3 different forms as AlO6, AlO5 and AlO4 depending on the coordination number in the structure. The average Al—O coordination number varies depending on the ratio of O/P. With the increasing ratio of O/P, the Al—O coordination number decreases, while the ratio of AlO6 in the structure decreases and the ratios of AlO5 and AlO4 increase. The fact that the AlO5 structural group is not as stable as AlO6 and AlO4 causes a decrease in the chemical resistance as a result of the increase in the amount of this group in the structure. It is thought that the time-dependent change in the dissolution behavior is caused by the change in the ratio of AlOx groups in the structure.
The changes in the pH value of the solvent during the dissolution of the glass samples obtained in the P2O5—CaO—Al2O3—Na2O—K2O system in 2% citric acid solution and distilled water medium are given in
When the results obtained were examined, it was observed that both samples increased the pH value of 2% citric acid solution and distilled water medium in the first stages of the dissolution. This situation is caused by the consumption of H+ ions in the solvent medium in accordance with the hydration reaction. With the progress of the dissolution, the ratio of H+ ion consumed decreased, and as a result of this, the increase in the pH value of the 2% citric acid solution slowed down. During the dissolution of the glass samples in distilled water, it was observed that the pH value stabilized after a while. This situation is caused by the fact that the ions passing from the glass structure to the solvent medium reach a level to form a buffer solution after a while.
As a result of the pH monitoring, it was determined that 2% citric acid solution did not cause a significant change in the pH value during the dissolution of the samples, and the pH value of the distilled water remained within the range of pH value required for the development of the tomato plant.
In the P2O5—CaO—SiO2—Al2O3—Na2O—K2O system, in order to examine the change in the physical properties of glass samples with the SiO2 component (SiO2/Na2O+K2O) added to the structure in response to the decreasing ratio of alkali oxide in equal amounts, the values of density, theoretical density, molar volume, oxygen molar volume and oxygen packing density were determined and given in Table 19. However, the changes in density, molar volume, oxygen molar volume and oxygen packing density depending on the SiO2 added to the composition are shown in
According to the calculated values of the theoretical density, the densities of the samples are expected to increase with an increasing ratio of SiO2/Na2O+K2O. However, when the experimental results were examined, it was observed that there was a decrease in the density with the increase of the ratio of SiO2 in the structure. With an increasing ratio of SiO2/Na2O+K2O in the composition, a decrease in the mass occurred. It is thought that the decrease in the density due to the introduction of SiO2 into the structure is caused by this situation. The molar volume value, on the other hand, showed a slight increase with the addition of SiO2 to the structure. This situation is caused by the decrease in the density.
When the calculated values of oxygen molar volume were examined, a decrease was observed in the oxygen molar volume with an increasing ratio of SiO2/Na2O+K2O. This situation is a result of the structure becoming more tightly packed as Si+4 (1.57) ion with high field strength replaces K+ (013) and Na+ (0.19) ions. The oxygen packing densities increased, as SiO2 replaced K2O and Na2O with ½ of the lower oxygen atoms.
The thermograms obtained as a result of the thermal analysis of the glass samples synthesized in the P2O5—CaO—SiO2—Al2O3—Na2O—K2O system are given in
When the obtained results were examined, it was determined that the glass transition temperature increased from 376° C. to 400° C. with the increase in the ratio of SiO2/Na2O+K2O. This increase observed in the glass transition temperature is a result of the formation of stronger bonds in the network structure as a result of the participation of SiO2 in the network structure formation in the form of [SiO4] tetrahedron.
The FTIR spectra of the glass samples synthesized in P2O5—CaO—SiO2—Al2O3—Na2O—K2O system are given in
When the spectrum obtained as a result of the structural analysis was examined, it was determined that the peak around 534 cm−1 represented the O═P—O or P—O—P bonds. With the addition of SiO2 to the structure, formation of a shoulder at the wave number of ˜499 cm−1 was observed, and it was determined that this was due to the bending vibrations of Si—O—Si and Si—O—P bonds. However, it was determined that the peaks, which were caused by the symmetrical vibrations of the P—O—P bonds and observed at the wave numbers of 710 cm−1, 757 cm−1 and 883 cm−1, were shifted to higher wave numbers with an increasing ratio of SiO2/Na2O+K2O. Wu et al. stated in their study that this is an indication of the formation of stronger bonds in the structure. However, it was determined that the peak at the wave number of ˜1103 cm−1 was shifted to a lower wave number with the addition of SiO2 to the composition, and it is thought that the reason for this situation may be the formation of the Si—O—P bonds in the structure. In addition, it was determined that the peaks observed around ˜980 cm−1, ˜1184 cm−1 were caused by the asymmetric vibration of the P—O—P bonds of the Q2 unit and the symmetrical vibration of the PO2− group of the Q2 unit, respectively and their intensity decreased with SiO2 added to the composition, and it was observed that the intensity of the peak at 1263 cm−1, which represents the asymmetric vibration of the PO2− group of the Q2 unit, increased.
The data obtained from the weight loss examinations of the glass samples synthesized in the P2O5—CaO—SiO2—Al2O3—Na2O—K2O system in 2% citric acid solution and distilled water medium, are given in
When the results obtained were examined, it was determined that the dissolution in distilled water medium proceeded faster with the addition of SiO2 to the composition, and it was determined that this was caused by the fact that the Si—O—P bonds in the structure were sensitive to the hydrolysis. On the other hand, when the dissolution behavior of the samples in 2% citric acid solution was examined, it was observed that the dissolution slowed down with the addition of SiO2 to the composition. Menaa et al. doped the silicophosphate glass with organic acids in their study and suggested that the organic-inorganic hybrid structure formed as a result of the presence of the carboxylic groups in the structure increases the chemical resistance by strengthening the Si—O—P bonds. This explains the slowing down the dissolution behavior in acidic medium with SiO2 added to the composition.
The changes in the pH value of the solvent during the dissolution of the glass samples obtained in the P2O5—CaO—SiO2—Al2O3—Na2O—K2O system in 2% citric acid solution and distilled water medium are given in
When the results obtained were examined, it was determined that the pH value of both solvent media increased as a result of the consumption of the H+ ion in the solvent in accordance with the hydration reaction in the first stages of the dissolution. It was observed that the increase in the pH value slowed down with the decrease of H+ ion consumed in the following stages of the dissolution in the solution of 2% citric acid. During the dissolution in distilled water, it was determined that the pH value of the solvent of the sample containing SiO2 began to decrease after 168 hours, and it was thought that this might caused by the deprotonation of the P—OH group formed as a result of the hydrolysis reaction, depending on the pH of the solution.
As a result of the pH monitoring carried out during the dissolution of the samples, it was determined that both samples did not cause a critical pH change for the development of the tomato plant in the solution of 2% citric acid and the pH value of the distilled water remained in a suitable range for the development of the tomato plant throughout the dissolution process. By evaluating the physical, thermal, structural analysis results and dissolution behavior of all synthesized samples, it was determined that the sample of P45C20S5A5N12.5K12.5 is the most suitable glass for the development of tomato plants. The selected sample of P45C20S5A5N12.5K12.5 was used as a glass fertilizer in the pot experiments with the tomato plants with and without additives (MnO2, Fe2O3, ZnO, B2O3, CuO, MoO3). The tomato plants were grown in 4 different soils containing no fertilizer, a glass a fertilizer, a glass fertilizer with a microelement additive and a chemical fertilizer (NPK) and as a result of the pot experiments, a glass fertilizer without a microelement additive showed the greatest improvement with a height increase of 12.3 cm and average leaf size of 3.01 cm. However, when the fruits obtained as a result of the pot experiments were examined, the weight and diameter values of the fruits obtained from the tomato plant grown in the pots without a fertilizer were determined to be 5.67 g and 22.09 cm, respectively, and it was determined that they had the highest grade when compared to the fruits of the other plants. As a result of the pot experiments carried out for over 60 days, it was observed that the glass fertilizer without a microelement additive had a promising effect on the development of the tomato plants.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021/007704 | May 2021 | TR | national |
This application is the national phase entry of International Application No. PCT/TR2022/050307, filed on Apr. 7, 2022, which is based upon and claims priority to Turkish Patent Application No. 2021/007704, filed on May 5, 2021, the entire contents of which are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/TR2022/050307 | 4/7/2022 | WO |
