A method for determining the content of basic lead carbonate, tribasic lead sulfate and tetrabasic lead sulfate in positive lead paste of lead-acid batteries

Abstract

The present invention belongs to the technical field of lead-acid batteries, and specifically relates to a method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in lead paste for positive electrodes of lead-acid batteries. The present invention solves the problem in the prior art that conventional heating methods cannot accurately determine whether moisture has been completely removed, resulting in incomplete moisture removal during heating or the weighed object reabsorbing some moisture from the air during the weighing process, leading to distorted measurement results. The present invention effectively differentiates and measures the contents of 3PbO·PbSO4·H2O and 2PbCO3·Pb(OH)2 by changing the weight of the lead paste at corresponding temperatures. The method can further determine the content of 4PbO·PbSO4 in combination with the test method for "GB T 23636-2017 Lead-acid Battery Plates," thereby obtaining the accurate contents of 3PbO·PbSO4·H2O, 4PbO·PbSO4, and 2PbCO3·Pb(OH)2.

Description

Technical Field

[0001] The invention belongs to the technical field of lead-acid batteries, and particularly relates to a method for determining the contents of basic lead carbonate, tribasic lead sulfate and tetrabasic lead sulfate in positive electrode lead paste of a lead-acid battery. Background Art

[0002] The components of the positive lead paste of lead-acid batteries have a significant impact on battery performance. The components of positive lead paste generally include: lead oxide, tribasic lead sulfate, tetrabasic lead sulfate, basic lead carbonate, free lead (metallic lead), and additives such as lead tetroxide and fiber. Currently, there are two main ways to test the components of positive lead paste: X-ray diffraction measurement (XRD); Refer to the provisions of 6.4.2 and 6.4.3 of GB T 23636-2017 Plates for Lead-acid Batteries; Refer to the requirements of 4.2 and 4.3 in HG / T 2340-2005 Tribasic Lead Sulfate.

[0003] However, these three methods have certain limitations, such as X-ray diffraction measurement is a semi-quantitative method, and the results are only informative, not precise metrological. X-ray diffraction results are significantly affected by sample selection and scanning point (XRD testing requires small sample sizes, typically less than 1 gram or even milligrams). For example, multiple test results for the same sample may show poor consistency, and the measured 4BS content may exceed the theoretical upper limit. The positive electrode paste of lead-acid batteries contains a variety of lead compounds. Possible stable components of the paste include PbO, PbSO₄, 3PbO·PbSO₄·H₂O, 4PbO·PbSO₄, 2PbCO₃∙Pb(OH)₂, Pb, and Pb₃O₄ (also containing a certain amount of H₂O). The diffraction peaks of these compounds overlap, making accurate analysis of the positive electrode paste composition difficult using XRD, and actual test results are suboptimal. Method 2 measures the positive electrode lead paste primarily as containing PbO and PbSO4. This method cannot distinguish between 3PbO·PbSO4·H2O and 4PbO·PbSO4, and therefore cannot determine the content of 3PbO·PbSO4·H2O and 4PbO·PbSO4. This method also fails to determine the content of 2PbCO3∙Pb(OH)2 and Pb3O4. Method 3 measures and calculates 3PbO·PbSO4·H2O based on the lead content (as PbO) and SO3. This method is suitable for higher-purity 3PbO·PbSO4·H2O, but it cannot confirm the composition of lead paste as 3PbO·PbSO4·H2O (it could also be 4PbO·PbSO4, PbO, PbSO4, etc.).

[0004] Therefore, the above methods have their own limitations and significant defects when used to measure the components of the positive lead paste of lead-acid batteries. Summary of the Invention

[0005] The present invention aims to overcome the aforementioned shortcomings of the prior art by providing a method for accurately analyzing the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in lead-acid battery positive electrode paste. This method can effectively differentiate and measure the contents of 3PbO·PbSO4·H2O and 2PbCO3·Pb(OH)2. Furthermore, the method can be combined with the test method in accordance with GB T 23636-2017, "Lead-Acid Battery Plates," to further determine the content of 4PbO·PbSO4, thereby accurately determining the contents of 3PbO·PbSO4·H2O, 4PbO·PbSO4, and 2PbCO3·Pb(OH)2.

[0006] The above object is achieved through the following technical solution: comprising the following steps:

[0007] 1. A method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in positive lead paste of lead-acid batteries, characterized by comprising the following steps:

[0008] 1) Take 2g-100g of unformed green plate lead paste sample.

[0009] 2) Weigh the crucible weight m 坩埚 , place the lead paste sample in a dry crucible, weigh the total weight of the crucible and the lead paste m0, the weight of the lead paste sample m 样品 = m0-m 坩埚 .

[0010] 3) Place the crucible containing the lead paste from step 2) in a high-temperature drying oven or heating furnace. Also place 100 ± 5 g of calcium oxide in the oven or heating furnace. Set the drying temperature T1 to 100°C-120°C and the drying time to 15-60 minutes. Apply power to heat the crucible for drying.

[0011] 4) After step 3) is completed, remove the crucible containing the lead paste and cool it to room temperature in a drying dish. Then weigh the total weight of the crucible and the lead paste, m1. After removing the crucible containing the lead paste, remove the calcium oxide and discard it.

[0012] 5) Place the crucible containing the lead paste from step 4) in a high-temperature drying oven or muffle furnace for drying. Simultaneously, place 100 ± 5 g of calcium oxide in the high-temperature drying oven or heating furnace. Set the drying temperature (T2) to 200°C-260°C and the drying time to 15-90 minutes for heating and drying.

[0013] 6) After step 5) is completed, remove the crucible containing the lead paste and cool it to room temperature in a drying dish. Then weigh the total weight of the crucible and the lead paste (m2). After removing the crucible containing the lead paste, remove the calcium oxide and discard it.

[0014] 7) Place the crucible containing the lead paste from step 6) in a drying oven or muffle furnace for drying. Simultaneously, place 100 ± 5 g of calcium oxide in a high-temperature drying oven or heating furnace. Set the drying temperature (T3) to 280°C-350°C and the drying time to 15-90 minutes for heating and drying.

[0015] 8) After step 7) drying is completed, remove the crucible containing the lead paste, cool it to room temperature in a drying dish, and then weigh the total weight of the crucible and the lead paste (m3). After removing the crucible containing the lead paste, remove the calcium oxide and discard it.

[0016] 9) Calculate the content of basic lead carbonate and tribasic lead sulfate in lead paste. The calculation method is as follows:

[0017] The weight of basic lead carbonate is expressed in m a Representative, molecular weight is M a Represents; the weight of tribasic lead sulfate is expressed in m （3BS） Representative, molecular weight is M （3BS） Representative; CO2 molecular weight is M （CO2） Represents; H2O molecular weight is M （H2O） represent.

[0018] m a = (m2-m3)* M a / M （CO2)

[0019] m （3BS） = [(m1-m2) / M （H2O） -(m2-m3) / M （CO2) ] *M （3BS）

[0020] The content of basic lead carbonate is expressed as X a Indicates that X a = m a / m 样品 *100%,

[0021] The content of tribasic lead sulfate is expressed as X （3BS） Representative, X （3BS） = m （3BS） / m 样品 *100%

[0022] 10) Calculate the content of tetrabasic lead sulfate in lead paste. The calculation method is as follows:

[0023] The molecular weight of tetrabasic lead sulfate is expressed as M（4BS） Representative; the molecular weight of lead sulfate is M （PbSO4） represent.

[0024] Take the sample lead paste from step 1) or the lead paste after weighing in step 8) and measure the lead sulfate content X according to 6.4.3 of GB T 23636-2017 Lead-acid Battery Plates. （PbSO4） .

[0025] Tetrabasic lead sulfate content is expressed as X （4BS） Representative, by the content of lead sulfate in the lead paste X （PbSO4） The data from step 9) can be obtained, X （4BS） =(X （PbSO4） -X （3BS） / M （3BS） * M （PbSO4） ) / M （PbSO4） * M （4BS） *100%.

[0026] The drying time of steps 3), 5), and 7) should be based on the fact that the weight of the lead paste no longer changes. The drying temperature T2 is preferably set in the range of 220°C-240°C, and the drying temperature T3 is preferably set in the range of 300°C-320°C.

[0027] Steps 4), 6), and 8) are preferably cooled to room temperature in a drying dish or a drying oven for 10 to 30 minutes.

[0028] The accuracy of the weighing instrument should reach 1 mg or 0.1 mg; the relative humidity of the storage space of the weighing instrument should be ≤25%; the lead paste sample size is preferably 20-50g.

[0029] The lead paste sample tested is the positive plate lead paste after curing and drying, or it can be the positive plate lead paste after mixing but not curing; the lead paste can be in block form or powder form.

[0030] In the prior art, thermogravimetric analysis is useful in studying the decomposition reaction of basic lead carbonate, but there is currently no mature method for measuring the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in lead paste using thermogravimetric analysis. The main reason is that conventional heating methods cannot accurately determine whether moisture has been completely removed, resulting in incomplete removal of moisture during heating, or the weighed object reabsorbs some moisture from the air during the weighing process, causing distortion of the measurement results. The method of the present invention can effectively distinguish and measure the contents of 3PbO·PbSO4·H2O and 2PbCO3·Pb(OH)2 by measuring the change in the weight of the lead paste at the corresponding temperature. It can also further determine the content of 4PbO·PbSO4 in combination with the test method of "GB T 23636-2017 Lead-acid Battery Plates", thereby obtaining the accurate contents of 3PbO·PbSO4·H2O, 4PbO·PbSO4, and 2PbCO3·Pb(OH)2. On the other hand, the sampling volume of the measurement method of the present invention is much larger than that of the three methods in the background art, which can overcome the problem of poor representativeness caused by too small a sampling volume. DETAILED DESCRIPTION

[0031] 1) Take 2g-100g of unformed green plate lead paste sample, preferably 20-50g.

[0032] 2) Weigh the crucible weight m 坩埚 , place the lead paste sample in a dry crucible, weigh the total weight of the crucible and the lead paste m0, the weight of the lead paste sample m 样品 = m0-m 坩埚 , the weighing accuracy should reach 1 mg or 0.1 mg.

[0033] 3) Place the crucible containing the lead paste from step 2) in a high-temperature drying oven or heating furnace for drying. Also place approximately 100g of calcium oxide in the high-temperature drying oven or heating furnace. Set the drying temperature T1 to 100°C-120°C and the drying time to 15-60 minutes.

[0034] 4) After drying in step 3), remove the crucible containing the lead paste and cool it to room temperature in a drying dish. Then weigh the total weight of the crucible and the lead paste (m1). After removing the crucible containing the lead paste, remove the calcium oxide and discard it.

[0035] 5) Place the crucible containing the lead paste from step 4) in a high-temperature drying oven or muffle furnace for drying. Simultaneously, place approximately 100g of calcium oxide in the high-temperature drying oven or heating furnace. Set the drying temperature T2 to 200°C-260°C for 15-90 minutes. The preferred range for drying temperature T2 is 220°C-240°C.

[0036] 6) After drying in step 5), remove the crucible containing the lead paste and cool it to room temperature in a drying dish. Then weigh the total weight of the crucible and the lead paste (m2). After removing the crucible containing the lead paste, remove the calcium oxide and discard it.

[0037] 7) Place the crucible containing the lead paste from step 6) in a drying oven or muffle furnace for drying. Simultaneously, place approximately 100g of calcium oxide in a high-temperature drying oven or heating furnace. Set the drying temperature T3 to 280°C-350°C for 15-90 minutes. The preferred range for drying temperature T3 is 300°C-320°C.

[0038] 8) After drying in step 7), remove the crucible containing the lead paste and cool it to room temperature in a drying dish. Then weigh the total weight of the crucible and the lead paste (m3). After removing the crucible containing the lead paste, remove the calcium oxide and discard it.

[0039] 9) Calculate the content of basic lead carbonate and tribasic lead sulfate in lead paste. The calculation method is as follows:

[0040] The weight of basic lead carbonate is expressed in m a Representative, molecular weight is M a Represents; the weight of tribasic lead sulfate is expressed in m （3BS） Representative, molecular weight is M （3BS） Representative; CO2 molecular weight is M （CO2） Represents; H2O molecular weight is M （H2O） represent.

[0041] m a = (m2-m3)* M a / M （CO2)

[0042] m （3BS） = [(m1-m2) / M （H2O） -(m2-m3) / M （CO2) ] *M （3BS）

[0043] The content of basic lead carbonate is expressed as X a Indicates that X a = m a / m 样品 *100%,

[0044] The content of tribasic lead sulfate is expressed as X （3BS） Representative, X （3BS） = m （3BS） / m 样品 *100%

[0045] 10) Calculate the content of tetrabasic lead sulfate in lead paste. The calculation method is as follows:

[0046] The molecular weight of tetrabasic lead sulfate is expressed as M （4BS） Representative; the molecular weight of lead sulfate is M （PbSO4） represent.

[0047] Take the sample lead paste from step 1) or the lead paste after weighing in step 8) and measure the lead sulfate content X according to 6.4.3 of GB T 23636-2017 Lead-acid Battery Plates. （PbSO4） .

[0048] Tetrabasic lead sulfate content is expressed as X （4BS） Representative, by the amount of lead sulfate in the lead paste X （PbSO4） The data from step 9) can be obtained, X （4BS） =(X （PbSO4） -X （3BS） / M （3BS） * M （PbSO4） ) / M （PbSO4） * M （4BS） *100%. Example

[0049] The weighing instrument used was an electronic balance with an accuracy of 0.1 mg.

[0050] The molecular formula of basic lead carbonate is 2PbCO3∙Pb(OH)2 or 3PbO∙2CO3∙H2O, with a molecular weight of 775.6;

[0051] The molecular formula of tribasic lead sulfate is: 3PbO·PbSO4·H2O, and the molecular weight is 990.87;

[0052] The molecular formula of tetrabasic lead sulfate is: 4PbO·PbSO4, and the molecular weight is 1196.02;

[0053] The molecular formula of lead sulfate is PbSO4, and the molecular weight is 303.26;

[0054] The molecular formula of carbon dioxide is CO2, and its molecular weight is 44.01;

[0055] The molecular formula of water is H2O, and its molecular weight is 18.02.

[0056] The above molecular weights are only selected values ​​for this embodiment, and it is recommended to refer to international standards.

[0057] 1) Take about 50g of each of the unformed green plate lead paste samples 1 and 2, and divide each sample into two portions (about 20g each), marked as sample 1-1, sample 1-2, sample 2-1, and sample 2-2 as shown in Table 1 below.

[0058] 2) Use an electronic balance (accuracy of 0.1 mg) to weigh the weight of the dried crucible used for each sample (m) 坩埚, place the lead paste sample in the corresponding dry crucible, weigh the total weight of the crucible and the lead paste m0, the lead paste sample weight m 样品 = m0-m 坩埚 , record the test data, the specific values ​​are shown in Table 1.

[0059] 3) Place the crucible containing the lead paste in step 2) in a drying oven for drying. Simultaneously, place 100g of calcium oxide in a high-temperature drying oven or heating furnace. Set the drying temperature T1 to 120°C and the drying time to 30 minutes.

[0060] 4) After drying in step 3), remove the crucible containing the lead paste and cool it to room temperature in a desiccating dish. Remove the calcium oxide and discard it. Then, weigh the total weight of the crucible and lead paste (m1) and record the test data. Specific values ​​are shown in Table 1.

[0061] 5) Place the crucible containing the lead paste in step 4) in a muffle furnace for drying. Simultaneously, place 100g of calcium oxide in a high-temperature drying oven or heating furnace. Set the drying temperature T2 to 230°C and the drying time to 50 minutes.

[0062] 6) After drying in step 5), remove the crucible containing the lead paste and cool it to room temperature in a desiccating dish. Remove the calcium oxide and discard it. Then, weigh the total weight (m²) of the crucible and lead paste and record the test data. Specific values ​​are shown in Table 1.

[0063] 7) Place the crucible containing the lead paste from step 6) in a muffle furnace for drying. Simultaneously, place 100g of calcium oxide in a high-temperature drying oven or heating furnace. Set the drying temperature (T3) to 310°C and the drying time to 50 minutes.

[0064] 8) After drying in step 7), remove the crucible containing the lead paste and cool it to room temperature in a drying dish. Remove the calcium oxide and discard it. Then weigh the total weight (m3) of the crucible and lead paste and record the test data. Specific values ​​are shown in Table 1.

[0065] 9) Calculate the content of basic lead carbonate and tribasic lead sulfate in lead paste. The calculation method is as follows:

[0066] The weight of basic lead carbonate is expressed in m a Representative, molecular weight is M a Represents; the weight of tribasic lead sulfate is expressed in m （3BS） Representative, molecular weight is M （3BS） Representative; CO2 molecular weight is M （CO2） Represents; H2O molecular weight is M （H2O） represent.

[0067] m a = (m2-m3)* M a / M （CO2)= (m2-m3)*775.6 / 44.01,

[0068] m （3BS） = [(m1-m2) / M （H2O） -(m2-m3) / M （CO2) ] *M （3BS） = [(m1-m2) / 18.02-(m2-m3 ) / 44.01]*990.87,

[0069] The content of basic lead carbonate is expressed as X a Indicates that X a = m a / m 样品 *100%,

[0070] The content of tribasic lead sulfate is expressed as X （3BS） Representative, X （3BS） = m （3BS） / m 样品 *100%. See Table 1 for specific values.

[0071] 10) Calculate the content of tetrabasic lead sulfate in lead paste. The calculation method is as follows:

[0072] Take the lead paste after weighing in step 8) and measure the lead sulfate content X according to 6.4.3 of GB T 23636-2017 Lead-acid Battery Plates （PbSO4） .

[0073] The molecular weight of tetrabasic lead sulfate is expressed as M （4BS） Representative; the molecular weight of lead sulfate is M （PbSO4） Representative, tetrabasic lead sulfate content is X （4BS） Representative, by the amount of lead sulfate in the lead paste X （PbSO4） The data from step 9) can be obtained, X （4BS） =(X （PbSO4） -X （3BS） / M （3BS） * M （PbSO4） ) / M （PbSO4） * M （4BS） =( X （PbSO4） -X （3BS） / 990.87* 303.26) / 303.26*1196.02. Specific values ​​are shown in Table 1. The contents of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in Table 1 are displayed to four decimal places. For the final calculated component percentage, it is recommended to use only two decimal places.

[0074] Table 1

[0075] Sample serial number Sample 1-1 Sample 1-2 Sample 2-1 Sample 2-2 <![CDATA[m 坩埚 ]]> 36.8826 40.1285 30.9108 38.7418 <![CDATA[m0]]> 57.401 60.2196 51.1165 59.1936 <![CDATA[m 样品 ]]> 20.5184 20.0911 20.2057 20.4518 <![CDATA[m1]]> 57.3012 60.1011 50.9159 58.8927 <![CDATA[m2]]> 57.2073 60.0198 50.7756 58.7523 <![CDATA[m3]]> 57.153 59.9677 50.7451 58.7296 ma 0.9569 0.9182 0.5375 0.4 <![CDATA[X a ]]> 4.6638 4.57 2.6602 1.9561 <![CDATA[m （3BS） ]]> 3.9408 3.2974 7.028 7.2091 <![CDATA[X （3BS） ]]> 19.206 16.4125 34.7823 35.2493 <![CDATA[X （PbSO4） ]]> 13.0167 12.9913 12.8973 12.9012 <![CDATA[X （4BS） ]]> 28.1539 31.4256 8.8817 8.3334

[0076] The above embodiments provide a detailed introduction to the method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in a positive lead paste of a lead-acid battery provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only intended to help understand the method of the present invention and its core idea. At the same time, for those skilled in the art, according to the ideas of the present invention, there may be changes in the specific implementation methods and application scopes. In summary, the contents of this specification should not be understood as limiting the present invention.

Claims

1. A method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in positive lead paste of lead-acid batteries, characterized in that: The following steps are involved: 1) Take 2g-100g of unformed green plate lead paste sample; 2) Weigh the crucible weight m 坩埚 , place the lead paste sample in a dry crucible, weigh the total weight of the crucible and the lead paste m0, the weight of the lead paste sample m 样品 =m0-m 坩埚 ; 3) Place the crucible containing the lead paste in step 2) in a high-temperature drying oven or heating furnace, and place 100±5g of calcium oxide in the high-temperature drying oven or heating furnace; set the drying temperature T1 to 100°C-120°C, the drying time to 15min-60min, and apply power to heat for drying; 4) After step 3) drying is completed, the crucible containing the lead paste is taken out, cooled to room temperature in a drying dish, and then the total weight of the crucible and the lead paste is weighed m1; after the crucible containing the lead paste is taken out, the calcium oxide is removed and discarded; 5) The crucible containing the lead paste in step 4) is placed in a high-temperature drying oven or a muffle furnace for drying. At the same time, 100±5g of calcium oxide is placed in the high-temperature drying oven or heating furnace. The drying temperature T2 is set to 200°C-260°C, and the drying time is 15min-90min, and heating and drying are performed. 6) After step 5) drying is completed, the crucible containing the lead paste is taken out, cooled to room temperature in a drying dish, and then the total weight of the crucible and the lead paste is weighed m2; after the crucible containing the lead paste is taken out, the calcium oxide is removed and discarded; 7) The crucible containing the lead paste in step 6) is placed in a drying oven or a muffle furnace for drying, and 100±5g of calcium oxide is placed in a high-temperature drying oven or a heating furnace; the drying temperature T3 is set to 280°C-350°C, and the drying time is 15min-90min, and heating and drying are performed; 8) After step 7) drying is completed, the crucible containing the lead paste is removed and cooled to room temperature in a drying dish, and then the total weight of the crucible and the lead paste is weighed m3; after the crucible containing the lead paste is removed, the calcium oxide is removed and discarded; 9) Calculate the content of basic lead carbonate and tribasic lead sulfate in the lead paste. The calculation method is as follows: The weight of basic lead carbonate is expressed in m a Representative, molecular weight is M a Represents; the weight of tribasic lead sulfate is expressed in m (3BS) Representative, molecular weight is M (3BS) Representative; CO2 molecular weight Represents; H2O molecular weight represent; The content of basic lead carbonate is expressed as X a Indicates that X a =m a / m 样品 *100%, The content of tribasic lead sulfate is expressed as X (3BS) Representative, X (3BS) =m (3BS) / m 样品 *100% 10) Calculate the content of tetrabasic lead sulfate in lead paste. The calculation method is as follows: The molecular weight of tetrabasic lead sulfate is expressed as M (4BS) Representative; the molecular weight of lead sulfate is M (PbSO4) represent; Take the sample lead paste from step 1) or the lead paste after weighing in step 8) and measure the lead sulfate content according to 6.4.3 of GB T 23636-2017 Lead-acid Battery Plates Tetrabasic lead sulfate content is expressed as X (4BS) Representative, by the content of lead sulfate in the lead paste With the data from step 9), 2. The method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in a positive lead paste of a lead-acid battery according to claim 1, wherein: The drying time of steps 3), 5), and 7) should be based on the fact that the weight of the lead paste no longer changes; the setting range of the drying temperature T2 is 220°C-240°C, and the setting range of the drying temperature T3 is 300°C-320°C.

3. The method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in a positive lead paste of a lead-acid battery according to claim 1, wherein: Steps 4), 6), and 8) are cooled to room temperature in a drying dish or a drying oven for 10 to 30 minutes.

4. The method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in a positive lead paste of a lead-acid battery according to claim 1, wherein: The accuracy of the weighing instrument should reach 1 mg or 0.1 mg; the relative humidity of the storage space of the weighing instrument should be ≤25%; the lead paste sample size should be 20-50g.

5. The method for determining the content of basic lead carbonate, tribasic lead sulfate, and tetrabasic lead sulfate in a positive lead paste of a lead-acid battery according to claim 1, wherein: The lead paste samples tested are cured and dried positive plate lead pastes, or mixed but not cured positive plate lead pastes; the lead pastes are in block or powder form.

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