Summary of the invention
The technical issues that need to address of the present invention just are to overcome the defective of prior art, a kind of method of measuring mishmetal solid solubility in the ferrous materials is provided, it can safer in laboratory study and production practices, reliably and at an easy rate realize the mensuration of rare earth solid solubility, has highly sensitive, the characteristics such as experimentation is safe, easy and experimental facilities and medicine are cheap and easy to get.
For addressing the above problem, the present invention adopts following technical scheme:
The invention provides a kind of method of measuring mishmetal solid solubility in the ferrous materials, described method is: select LiCl+TEA triethanolamine+ethylene glycol+diphenylguanidine+benzene 1.5% absolute ethyl alcohol electrolytic solution, carry out low-temperature electrolytic, then the solid solution rare earth is separated with rare earth second-phase snotter and utilizes after treatment spectrophotometer to carry out assay.
Concrete steps are:
(1) electrolysis: the percentage by weight proportioning of electrolytic solution is: 2% LiCl, and 2% TEA triethanolamine, 0.5% ethylene glycol, 0.2% diphenylguanidine, 1.5% benzene, surplus is absolute ethyl alcohol;
Anode is the ferrous materials electrolytic sample of mishmetal during electrolysis, and negative electrode is stainless-steel tube; Weigh and record before the sample electrolysis, electrolysis temperature is-5 ℃~-10 ℃, and after electrolysis 2-3 hour, powered-down takes out sample, and weighs after drying, and the variation of front and back weight is the mass M that sample consumes;
(2) separate solid solution rare earth and rare earth second-phase snotter: by filling up at a slow speed quantitative filter paper of 4-6 layer in the Buchner funnel, electrolytic solution after the electrolysis is poured in the Buchner funnel, with preservative film the leak mouth is sealed again, carry out isolated by filtration, get the electrolytic solution filtrate of filtering and impurity removing;
(3) volatilization, dissolving, adjust pH: electrolytic solution filtrate 85 ℃ of lower implementations the in thermostat water bath to filtering and impurity removing are volatilized, and remove lower boiling organism; Again dissolve with deionized water, add hydrochloric acid, destroy residual organic substances and regulate acidity making the pH value be 1-2, surveying the filtrate cumulative volume is V;
(4) be H type strong cation-exchanging resin making the transition, the ion exchange column of packing into, from the filtrate cumulative volume, take out for the treatment of volume be V
1Filtrate, with its slow ion exchange column, make that all ions are all adsorbed by this resin in the solution, be that the hydrochloric acid flushing of 1.7N-2.0N is removed Fe, Mn, Al 2-3 time with concentration then; Hydrochloric acid wash-out take concentration as 4.3N-5.0N obtains pure rare-earth ion solution again;
Regulate acidity and make the pH value for 1-2, get liquid to be measured, the survey volume is V
2
(5) prepare the standard lean solution of one group of concentration known with the rare earth titer, adding 3ml, 0.02%wt Chlorophosphonazo III solution obtain 25ml Comparison of standards solution as developer, measure their absorbance with spectrophotometric, drawing standard working curve, the slope of standard working curve are K;
(6) oxalic acid of 10ml, 10%wt and the Chlorophosphonazo III solution of 3ml, 0.02%wt will be added in a certain amount of liquid to be measured, supply liquid to be measured and obtain 25ml solution to be measured, shake up rear with its absorbance A of spectrophotometer measurement, with thickness be b cuvette, do reference with reagent blank, recycle drawn standard working curve and can calculate the concentration of solution Rare Earth Ion, obtain the solid solubility of rare earth element in ferrous materials.
The solid solubility computing formula of rare earth element in ferrous materials is:
In the formula: A is the absorbance of liquid to be measured, and V is the filtrate cumulative volume behind volatilization, dissolving, the adjust pH, V
1For from the filtrate cumulative volume, take out for the treatment of the volume of filtrate, V
2Be the liquor capacity of collecting after handling, K is the slope of standard working curve, and b is the thickness of cuvette, and M is the quality that sample consumes when electrolysis.
Anode iron clamp and sample contact position can not be immersed in the electrolytic solution when electrolysis.
The standard lean solution of preparing one group of concentration known with the rare earth titer has 4 kinds of concentration at least.
The electrolytic solution universality that the present invention selects is better, stable reaction.
Quantitative filter paper isolated by filtration rare earth second-phase snotter, nonaqueous electrolytic solution water-bath are evaporated away low-boiling-point organic compound and the not volatile substance that stays are dissolved, add hydrochloric acid again with deionized water and destroy organism and cross strong cation-exchanging resin and get rid of the interfering ions such as Fe, Mn, Al at a slow speed by-5 ℃~-10 ℃ low-temperature electrolytics, 4~6 layers in the present invention, obtain pure rare-earth ion solution, measure the content of mishmetal solid solubility in the ferrous materials for spectrophotometer.
The present invention can safer in laboratory study and production practices, reliably and at an easy rate realize the mensuration of rare earth solid solubility, can reach highly sensitive, the characteristics such as experimentation is safe, easy and experimental facilities and medicine are cheap and easy to get.
Embodiment
Concrete steps are:
(1) electrolysis: the percentage by weight proportioning of electrolytic solution is: 2% LiCl, and 2% TEA triethanolamine, 0.5% ethylene glycol, 0.2% diphenylguanidine, 1.5% benzene, surplus is absolute ethyl alcohol;
Anode is the ferrous materials electrolytic sample of mishmetal during electrolysis, and negative electrode is stainless-steel tube; Weigh and record before the sample electrolysis, electrolysis temperature is-10 ℃, and after electrolysis 2-3 hour, powered-down takes out sample, and weighs after drying, and the variation of front and back weight is the mass M that sample consumes; Anode iron clamp and sample contact position can not be immersed in the electrolytic solution when electrolysis.
(2) separate solid solution rare earth and rare earth second-phase snotter: by filling up at a slow speed quantitative filter paper of 4-6 layer in the Buchner funnel, electrolytic solution after the electrolysis is poured in the Buchner funnel, with preservative film the leak mouth is sealed again, carry out isolated by filtration, get the electrolytic solution filtrate of filtering and impurity removing;
(3) volatilization, dissolving, adjust pH: electrolytic solution filtrate 85 ℃ of lower implementations the in thermostat water bath to filtering and impurity removing are volatilized, and remove lower boiling organism; Again dissolve with deionized water, add hydrochloric acid, destroy residual organic substances and regulate acidity making the pH value be 1-2, surveying the filtrate cumulative volume is V;
(4) be H type strong cation-exchanging resin making the transition, the ion exchange column of packing into, from the filtrate cumulative volume, take out for the treatment of volume be V
1Filtrate, with its slow ion exchange column, make that all ions are all adsorbed by this resin in the solution, be that the hydrochloric acid flushing of 1.7N-2.0N is removed Fe, Mn, Al 2-3 time with concentration then; Hydrochloric acid wash-out take concentration as 4.3N-5.0N obtains pure rare-earth ion solution again;
Regulate acidity and make the pH value for 1-2, get liquid to be measured, the survey volume is V
2
(5) prepare the standard lean solution of one group of concentration known with the rare earth titer, have 4 kinds of concentration at least, add respectively 3ml, 0.02%wt Chlorophosphonazo III solution obtains one group of 25ml Comparison of standards solution as developer, measure their absorbance with spectrophotometric, drawing standard working curve, the slope of standard working curve are K;
(6) oxalic acid of 10ml, 10%wt and the Chlorophosphonazo III solution of 3ml, 0.02%wt will be added in a certain amount of liquid to be measured, supply liquid to be measured and obtain 25ml solution to be measured, shake up rear with its absorbance A of spectrophotometer measurement, with thickness be b cuvette, do reference with reagent blank, recycle drawn standard working curve and can calculate the concentration of solution Rare Earth Ion, obtain the solid solubility of rare earth element in ferrous materials.
The solid solubility computing formula of rare earth element in ferrous materials is:
In the formula: A is the absorbance of liquid to be measured, and V is the filtrate cumulative volume behind volatilization, dissolving, the adjust pH, V
1For from the filtrate cumulative volume, take out for the treatment of the volume of filtrate, V
2Be the liquor capacity of collecting after handling, K is the slope of standard working curve, and b is the thickness of cuvette, and M is the quality that sample consumes when electrolysis.
This method measures that to add total amount of rare earth be that the rare-earth solid solution capacity of the CSP mild carbon steel hot rolled plate of 135ppm is 10.6ppm.
It should be noted that at last: obviously, above-described embodiment only is for example of the present invention clearly is described, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give all embodiments exhaustive.And the apparent variation of being amplified out thus or change still are among protection scope of the present invention.