Huang Kai, Wang Dianzuo, Huang Qinping
Antimony ore often contains a certain amount of arsenic, and the separating stibnite pyrite arsenic, antimony ore flotation process is needed to solve the problem.Many properties of strontium and arsenic are similar, but the mineral crystal structure of bismuth ore (Sb 2 S 3 ) and arsenic pyrite (FeAsS) are not the same [1] . The stibnite is an A 2 X 3 type compound with a chain-like crystal structure. The distance of the Sb-S in the chain is 2.5 Ã…, and the distance between the two chains is about 3.2 Ã…. The bond force is weakened and easy to follow. This direction dissociates. The arsenic pyrite is a pyrite family, which is an AX 2 type compound, and X 2 is AsS. Like S 2 in pyrite, it is a dumbbell-shaped anionic crystal structure with a strong total between S-As. a bond, a very short distance, metal cations and anions also the distance between the short compact crystalline structure, similar to the force in each direction key. Due to the weak bond strength of the cleavage (or rupture) surface, the stibnite has a certain natural floatability and is easily dissolved in an alkaline solution. The crystalline structure of arsenopyrite is the same as that of pyrite. The flotation characteristics are close to that of pyrite. For example, it is selective for some collectors , easy to oxidize and reduces floatability. Therefore, it is possible to achieve the purpose of separation flotation by finding a selective collector, utilizing the difference in floatability of stibnite and arsenic pyrite in an alkaline medium, and the difference in oxidation rate.
In this study, a modified Harrison flotation tube [2] was used to conduct a selective collector, 2 alkaline slurry flotation, 3 oxidation and then flotation experiments on stibnite and arsenic pyrite. The laboratory flotation machine carried out a separation flotation test on arsenic-containing strontium sulfide ore, and obtained satisfactory results, which was confirmed in production practice.
In this study, electrophoresis microscopy [3] Measurement of the ζ potential of the stibnite, ultraviolet absorption spectroscopy [4] Measurement xanthate, dixanthogen adsorption amount stibnite and arsenopyrite surface and Product of action.
In this paper, the mechanism of these three separation flotation methods was studied separately. The electric double layer model and surface chemical reaction products of stibnite in acid and alkali solution were discussed. The relationship between various ion concentrations and pH in solution was plotted. The pMe-pH diagram discusses the relationship between these properties and the floatability of minerals.
First, the test method
1, sample
The stibnite mine is taken from the Banxi antimony ore. The arsenic pyrite is taken from the Yaogangxian tungsten mine. It is manually selected, hammered to -3 mm and then ground into a porcelain ball mill . The 80 mesh standard sieve is dried and the standard is 200 mesh. Screen the wet sieve and take -80 + 200 mesh size as a sample. Stibnite dried after washing with distilled water, after treatment with hydrochloric acid 1:1 arsenopyrite repeatedly washed with distilled water to a solution of C1 - disappears, filtered and dried in a vacuum oven. Both were placed in a jar and placed in a desiccator. Each test sample was weighed out with a weighing bottle. The sample for zeta potential measurement was further ground to -5 μm by agate . The content of minerals (Sb 2 S 3 ) in stibnite is 96.8%; the content of minerals (FeAsS) in arsenic pyrite is 97.8%.
2. Pharmacy
The flotation collectors Dinghuang medicine, butyl ammonium black medicine, ethyl sulfur nitrogen, and amine alcohol yellow medicine are all industrial products. The xanthate and the xanthate used in the absorption spectroscopy were purified. Diethyl ether, antimony trichloride, sulfuric acid, sodium hydroxide, potassium permanganate, copper sulfate and other analytical grade. The experiment used once distilled water, and the zeta potential and absorption spectrum were measured using double distilled water.
3. Test method
All mineral flotation tests were carried out in a modified Harrison tube, and a laboratory XFD type 1.5 liter flotation machine was used for the ore flotation test. The zeta potential was measured using a Japanese MRK microelectrophoresis apparatus. The ultraviolet absorption spectrum was measured by a domestic type 751 spectrophotometer. The pH was measured with a pHS-2 type acidity meter. The conductivity meter was measured with a DDS-11 type conductivity meter.
The improved Harrison flotation tube was fixed at 17.5 ml/min. The standard mean square error of the flotation test is σ ^ s =1.28%. 1 g of the ore sample is used for each test. The slurry is directly adjusted in the flotation tube, wetted with the pre-formed pH solution, and stirred for 0.5 minutes. Add the conditioning agent (add as necessary, adjust the slurry for a specific time), adjust the slurry for 1.5 minutes, and float for 4 minutes.
The electrophoresis tank of the microelectrophoresis apparatus is rectangular (75 × 25 × 3 mm, inner thickness 1 mm). Position of the stationary layer (Y)
It is represented by the following formula:
d is the groove depth (ie inner thickness). The calculation of the zeta potential is performed as follows:
Ζ-moving potential, mV; dielectric constant of D-water, D=80; n-viscosity coefficient, 25°C, n=0.00894 poise; S-electrophoresis trough cross-sectional area, S=0.1403cm 2 ; Distance moved, μm; time of t-particle movement, seconds; conductivity of C-solution, mΩ/cm; i-current, mA.
The determination products of the interaction products of xanthate and double xanthate with stibnite and arsenic pyrite are the products of the mineral surface after being washed by the flotation conditions, and after washing twice, the surface of the mineral is dissolved with pure ether. . After centrifugation, the supernatant was transferred to a quartz cuvette and placed in a Model 751 spectrophotometer.
Second, the test results
The separation of stibnite and arsenic pyrite was studied by three schemes: 1. Selective collector method; 2. Alkaline slurry method; 3. Oxidation method. The results are as follows.
1. Selective collector method
To selectively collector stibnite, with butyl ammonium aerofloat (C 4 H 9 O) 2 PSS-NH 4, of diethyl dithiocarbamate (C 2 H 5) 2 NCSSNa , sphingosine xanthate (C 2 H 5) 2 NCH 2 CH 2 OCSSNa so on stibnite and arsenopyrite flotation tests carried out, and Ding C 4 H 9 OCSSNa xanthate as collector for comparison.
1) Ding Huang Yao
Ding xanthate is usually used as a collector for flotation of stibnite. When using Dinghuang, the relationship between the floatability and pH of stibnite and arsenopyrite is shown in Fig. 1. The bismuth ore has the best floatability at pH<5, the floatability decreases sharply at pH 5-7, and the floatability is poor at pH 7-11. The arsenic pyrite has good floatability before pH 6. The floatability decreases linearly at pH 6-11, and pH>11 is almost completely inhibited. Both minerals are buoyant at pH < 5, and pH > 8 is not good. In the range of pH 6-8, arsenic pyrite is better than stibnite, but the difference is not significant. Therefore, as has long been shown in production practice, it is difficult to directly separate strontium-arsenic with dicofin as a collector.
Fig.1 Recovery of antimonite and arsenopyrite
As a function of pH with butyl xanthate(10 mg/1)
2) Butyl ammonium black medicine
Figure 2 is a graph showing the relationship between the floatability of stibnite and arsenopyrite and pH when butyl is used as a collector. Ding according to the black drug has a strong ability to capture stibnite, and the ability to capture arsenic pyrite is weak, especially in the medium with pH<4, and has certain selectivity for bismuth-arsenic separation flotation.
Fig.2 Recovery of antimonite and arsenopyrite as a function
Of pH with dibutyl dithio-phosphate ammonium(10mg/1)
3) Ethyl sulfide
The capture performance of ethionine to stibnite and arsenopyrite is shown in Fig. 3. The stibnite has good floatability in the range of pH 5-10. At all pH values, ethyl sulphide nitrogen has a weak ability to capture arsenic pyrite. Therefore, ethyl sulphide is a collector with good selectivity for stibnite and arsenopyrite. It is particularly noteworthy that the yellowing and black medicines have a significantly lower floatability of the stibnite after pH>5, while the ethylsulfide nitrogen has a high recovery rate below pH9.
Fig.3 Recovery of antimonite and arsenopyrite as a function of
pH with diethyl dithiocarbamate sodium (10m/1)
4) Amino alcohol xanthate
The relationship between the floatability of stilbite and arsenic pyrite and pH is shown in Figure 4. The arsenopyrite cannot be effectively floated in all pH ranges. Yankuang has good floatability in media with pH<6. Therefore, the aminoglycoside is also a selective collector.
In addition, also in a vinegar thiamine (CH 3) 2 CHOCSNHC 2 H 5, yellow eyes butyl acetate C 4 H 9 OCSSC 2 H 4 CN as collector flotation test. However, the separation and flotation effect of bismuth-arsenic is not good.
Fig.4 Recovery of antimonite and arsenopyrite as a function of
pH with diethyl aminoethyl dithiocarbonate sodium (10 mg/1)
2. Alkaline pulp separation flotation method
When Dinghuang is a collector, the unactivated stibnite and arsenopyrite are not good in buoyancy in alkaline media (see Figure 1). However, there is a small amount of activator (CuSO 4 1.5mg / l), arsenic pyrite is very buoyant in alkaline medium, and stibnite is still not floating, see Figure 5, which can achieve cesium-arsenic separation flotation the goal of.
It can be seen that the conditions for the bismuth-arsenic separation flotation in the alkaline slurry should be activated first. The surface of Cu 2+ -activated arsenopyrite has similar floatability to copper minerals, and the recovery rate is high in all pH ranges, almost a flat straight line. However, the stibnite in the alkaline medium is not conducive to the activation of Cu 2+ due to the surface dissolution behavior, and is not conducive to the collection of the anion collector, but is inhibited, which will be further discussed below.
Fig.5 Recovery of antimonite and arsenopyrite as a function
Of pH with butyl xanthate (10 mg/1) CuSO 4 ·5H 2 O (1.5mg/1)
3. Oxidative separation flotation method
The effect of the amount of oxidant potassium permanganate and its stirring time on the floatability of stibnite and arsenopyrite is shown in Fig. 6 and Fig. 7.
It can be seen from Fig. 6 that arsenic pyrite is easily oxidized. As the amount of oxidant increases, the recovery rate of arsenic pyrite decreases rapidly; at the same time, stilbite is not easily oxidized, and the recovery rate decreases little. When the concentration of potassium permanganate is 4×10 -5 to 1×10 -4 mol/L, the difference in the floatability of bismuth and arsenic is the largest.
Figure 7 shows that the oxidation time is very important. When the stirring time is 0.5 minutes, the arsenopyrite is strongly inhibited, and the stibnite is floated better. After half a minute, the inhibition of arsenopyrite was weakened, and by 15 minutes, the arsenopyrite floated better. It can be seen that the amount of oxidant and the time of action are important and must be strictly controlled, otherwise it is difficult to achieve the desired effect.
▲ CK MnO 4 ×10 -5 mol/l
Fig.6 Effect of potassium permanganate on the flotation antimonite
And arsenopyrite with butyl xanthate (10 mg/1) pH 3.2
Fig.7 The effect of conditioning time on flotation
Recovery of antimonite and arsenopyrite with butyl
Xanthate (10 mg/1) and KMnO 4 (4.2×10 -5 mol/1)
4. Separation and flotation of arsenic-containing antimony sulfide ore
According to the above separation route, this study used a selective collector method and an alkaline slurry method for the separation of flotation of arsenic-containing strontium ore in a certain area. The test used a 1.5-liter XFD-63 single-tank flotation machine for grinding. The fineness is 68%-200 mesh, and the test results are shown in Table 1. It can be seen from the table that the arsenic content of the antimony concentrate is as high as 4.33%. Using the butyl ammonium black drug selective collector method, high-quality antimony concentrate can be obtained by rough selection, the niobium grade is 56.10%, the arsenic content is only 0.34%, and the radon recovery rate is 95.61%. The crude concentrate obtained by the flotation of the lead xanthate collector by the action of lead nitrate is selected by the alkaline slurry method for the separation of antimony-arsenic separation and anti-flotation, and the fine antimony concentrate and arsenic concentrate can also be obtained. The concentrate grade is 55.59%, the recovery rate is 94.81%, the arsenic content is 0.66%; the arsenic concentrate grade is 29.15%, the recovery rate is 80.28%, and the 锑 is 2.78%. It can be seen that satisfactory results can be obtained by either the selective collector method or the alkaline slurry method. Separation and flotation of alkaline pulp can obtain two concentrates (锑 concentrate and arsenic concentrate), but the quality of antimony concentrate is not as high as that of selective collector, and the process is more complicated.
â–² Table 1 Results of flotation test of arsenic-containing antimony ore (%)
experiment method | Raw ore | Antimony concentrate | Arsenic concentrate | |||||||
A, conventional flotation: Dinghuang, lead nitrate, rough selection B. Selective collector method: butyl ammonium black drug, lead nitrate, rough selection C. Alkaline pulp method: Dinghuang medicine, lead nitrate, rough selection, basic slurry anti-flotation selection | grade | grade | Recovery rate | grade | Recovery rate | |||||
Sb | As | Sb | As | Sb | As | Sb | As | Sb | As | |
5.17 | 0.46 | 48.91 | 4.33 | 94.78 | 94.14 | |||||
5.19 | 0.55 | 56.10 | 0.34 | 95.61 | 5.48 | |||||
5.01 | 0.45 | 55.59 | 0.66 | 94.81 | 12.63 | 2.78 | 29.15 | 0.69 | 80.28 |
Third, discussion
1. In the different acid-base pulps of stibnite, the flotation recovery rate of Dingxuan as collector is one-to-one corresponding to its zeta potential adsorption amount of xanthate, see Figures 8 and 9.
Fig.8 The effect of pH on adsorption xanthate and flotation of antimonite
When the pH is <5, the zeta potential is high (the negative value is small), the adsorption amount to the xanthate is large, and the recovery rate of the stibnite is high. As the pH value increases, the zeta potential and the amount of xanthate adsorbed decrease, and the recovery rate of stibnite decreases accordingly. The rate of change is the highest at pH 5 to 6, and then slow. These changes depend on the dissolution state of the stibnite surface.
In the acidic solution, the surface of Sb 2 S 3 is dissolved into Sb 3 + and S 2 - , and the reaction formula is
Sb 2 S 3 (solid) ↔ 2Sb 3 + +3S 2 - (1)
The electric double layer is positioned ten ions mainly Sb 3, S 2 -, and HS -.
Fig.9 Zeta-potential of antimonite as function pH
In an alkaline solution, the reaction of the surface of the stibnite is
2Sb 2 S 3 (solid) + 4OH - ↔ SbO +3SbS +H 2 O (2)
The double layer positioning ions are mainly SbO , SbS Wait.
According to the above (1), (2) reaction formula, free 焓ΔF according to the formation of each component (Sb 2 S 3 =-32, OH - = -37.6, SbO = -82.5, SbS = -13, H 2 O = -56.7 Kcal / mol) [5] and the solubility product K sp Sb 2 S 3 is = 2.9 × 10 -59 [6] , is calculated by Sb 3+ solution thermodynamics, SbO , SbS The relationship between ion concentration and pH is plotted as a pMe-pH map (see Figure 10). The intersection of the two lines in the figure is pH= 5, 1gC=10 -5 . When pH<5, Sb 3+ ions predominate, which is beneficial to the adsorption of anion collector and lead to flotation; when pH>5, SbO And SbS Ions dominate and impede the adsorption and flotation of the anion collector. This is consistent with the changes in the surface zeta potential of the stibnite, the amount of xanthate adsorbed, and the flotation recovery ε. This may be the reason why the recovery rate of pH<5 is high in the flotation of the yellow medicinal herbs in the stibnite mine, and the floating in the alkaline medium is not good.
Fig.10 Diagram of log (C)- pH in antimonite-water system
It can be seen from Fig. 9 that the zeta potential curve II on the surface of the stibnite after the addition of xanthate is almost the translation of the zeta potential curve I when no xanthate is added, which can be considered as the hydrocarbon chain adsorbed on the mineral surface after the addition of xanthate. The electrical center of the longer butyl xanthate is increased by a certain distance from the ionic radius before the addition of xanthate. In the alkaline solution, as the pH increases, the curve II gradually closes to the curve I, which is the SbO in the alkaline medium. , SbS More and more, the amount of xanthate adsorbed is becoming less and less characterized.
2. According to the study of the reaction between sulfuric acid and sulfide ore by Poling [7] and Woods [8] , when the concentration of ethyl xanthate is 6.25 x 10 -4 mol/L, pH=7, the glow is determined. The electrostatic potential of the antimony ore is -0.125 volts or -0.09 volts; the electrostatic potential of the arsenic pyrite is +0.22 volts. The former is smaller than the reversible potential of the xanthate (+0.13 volts). It is not easy to be oxidized to double xanthate. The surface of stibnite is mainly formed by the adsorption of xanthate, while the latter is larger than the oxidation potential of xanthate. The product of its action should be mainly dihuang.
In this study, flotation experiments were carried out on stibnite and arsenic pyrite with dicamba and butyl-xanthine respectively. When the bismuth ore and arsenite were floated with double xanthate, similar recovery was obtained. (55% and 52%), the recovery ability of xanthate to stibnite is stronger than that of arsenic pyrite, and the recovery rate of stibnite is 15% larger than that of arsenite. Conversely, the ability of Shuanghuang to capture arsenic pyrite is stronger than that of stibnite, which is consistent with the above discussion. However, it should be added that the surface of the stibnite is not only adsorbed by the xanthate state, but also may be adsorbed by the double xanthate; likewise, the surface of the arsenic pyrite is both xanthate and xanthan. Adsorbate in the acid state. After the interaction of xanthate and xanthate with stibnite and arsenic pyrite, respectively, the product obtained by dissolving with diethyl ether was confirmed by UV absorption spectroscopy (see Figures 11 and 12). When xanthate is used together with stibnite and arsenic pyrite, the product has obvious absorption peak of double xanthate at 240mμ; and the effect of double xanthate with stibnite and arsenopyrite respectively. The product, in addition to the absorption peak of the double xanthate, also has obvious absorption peaks of xanthate and xanthate (wavelength 310rnμ). The xanthate and the xanthate are converted to each other and may be adsorbed to the surface of the mineral after conversion in solution or may occur on the surface of the mineral.
Fig.11 UV. absorb-spectra of reactive products
Of xanthate on antimonite and arsenopyrite
Fig.12 UV. absorb-spectra of reactive products
Of dixanthogen on antimonite and arsenopyrite
According to a recent study by Jones and Woodcock [9] , there is a variety of reactions in the decomposition of sodium xanthate in aqueous solution: decomposition into xanthate ion ROCSS - , xanthate ion ROCSSO - , monothiocarbonate ion ROSCO in alkaline solution - and S 2 - , S 0 ; can be decomposed into CS 2 and OCS in an acidic solution, and vary greatly at different pH values ​​and at different times. In the presence of nucleophilic atoms, the xanthate absorption peaks are formed. very obvious. From this, we can understand the product of the effect of Shuanghuang medicine with stibnite and arsenic pyrite, and the obvious absorption peak in the wavelength range of xanthate and xanthate. According to the thermodynamic calculation of КаковÑкий [10] , there is also the possibility of producing xanthate and diphtheria on the mineral surface.
3. Arsenic pyrite is easily oxidized like pyrite. According to previous research reports, the products may be FeO (OH) and FeAsO 4 to form a hydrophilic layer, which reduces the floatability. As the amount of oxidant increases, the oxidation increases and the recovery rate decreases rapidly.
The stibnite after three months of oxidation in the air is as good as the newly ground stibnite. According to research by Finkelstein et al. [11] , it is believed that after exposure to air, the sulfur concentration on the surface of the stibnite increases. The surface sulfur concentration of the freshly ground stibnite is 0.2 monolayers, and after oxidation for three months, it is 9- 12 monolayers, thus maintaining its floatability. Figure 6 also shows that stibnite is not easily oxidized. Under the action of oxidant, the degree of oxidation of stibnite is always much lighter than that of arsenite, and the buoyancy increases with the increase of stirring time. Therefore, using the difference in oxidation degree and rate of arsenic pyrite and stibnite, separation flotation of stibnite and arsenic pyrite can also achieve certain effects.
Fourth, the conclusion
1. This study gives three ways of separation and flotation of stibnite and arsenic pyrite: 1 Selective collector method, the ability of butylammonium black, ethyl sulphide and sulphate to capture stibnite Strong, the ability to capture arsenic pyrite is weak, is a selective collector for cesium-arsenic separation flotation; 2 alkaline ore method, when dicamba is a collector, in alkaline medium Adding an appropriate amount of activator can activate the arsenic pyrite to float upward, while the stibnite does not float, thereby achieving the purpose of bismuth-arsenic separation flotation; 3 oxidation method, arsenic pyrite is easily oxidized and inhibited, and stilbene The ore is not easy to oxidize, has good floatability, and can be used for strontium-arsenic sorting.
Flotation tests were carried out on the arsenic-containing antimony sulfide ore by selective collector method and alkaline slurry method, and satisfactory results were obtained. Among them, the butyl ammonium black drug selective collector method was used for flotation, and the antimony concentrate contained Sb. 56.10%, As 0.34%, 锑 recovery rate 95.61%; Dinghuang medicine alkaline slurry method flotation, strontium concentrate containing Sb 55.59%, As 0.66%, hydrazine recovery rate 94.81%, arsenic concentrate containing As 29.15%, containing Sb is 2.78% and arsenic recovery is 80.28%. These results have been verified in production practice.
2. There is a corresponding relationship between the zeta potential of the stibnite in the aqueous solution of different pH values, the adsorption amount of xanthate and the flotation behavior. According to the experimental results, two types of dissolution, dissociation and hydration reactions occur in the aqueous solution of stibnite at pH=5. The calculations and diagrams of thermodynamics are consistent with the experimental results. It is thus determined that two types of electric double layer models and different localized ions in the slurry of stibnite can better explain the flotation phenomenon and provide a theoretical basis for the separation of strontium-arsenic flotation.
3. Studies have shown that the product of the interaction between Dinghuang and stibnite may be mainly the adsorption of bismuth xanthate, but also the adsorption of Shuanghuang. The product of interaction with arsenite is mainly Shuanghuang. The adsorption of xanthate type.
references
[1] Wang Zhengran, Chen Wu, Mineralogy, Shanghai Science and Technology Press, 1965, p170-205
[2] Huang Kaiguo, the newly improved foamless flotation tube and its device, Journal of Central South Institute of Mining and Metallurgy, 1980, No4, p107-111
[3] Mori, et al., Improved method for determining the strontium potential of ore by microelectrophoresis, foreign metal ore dressing , 1981, No9, P 13-23
[4] Wang Dianzuo, Principles and Applications of Flotation Agents, Metallurgical Industry Press, 1982, p355-357
[5] RM Garrels, CL Christ, Solutions, Minerals, and Equilibria, New York 1965, p.403-428
[6] Tao Kun translation, Soviet Chemistry Handbook (III), Science Press, 1963, P.557
[7] GW Poling, Reaction between Sulfur Hydrogens and Sulfide Minerals, Flotation, Vol., Metallurgical Industry Press, 1981, p.264
[8] R. Woods, Electrochemistry, Flotation, Vol., Metallurgical Industry Press, 1981, p214.
[9]M. H. Jones, JT Woodcock, Decomposition of Alkyl Dixanthogens in Aqueous Solutions, Inter, Jou r. Mineral process, 1983.vo1.10, No1, p.1-24
[10] И. Ð. КаковÑкий, P. H. Шекалева, О примении физнко-ХИмичеÑких методов иÑледованиÑÑ… по теории Флотации, ТеоретичеÑкие оÑновы и контроль процеÑÑов флотации, МоÑква, 1980, p94.
[11] NP Finkelstein et al., Natural hydrophobicity and induced hydrophobicity of sulfide mineral systems, flotation theory - wetting and flocculation, Hunan Institute of Science and Technology Information, June 1981, p.19-34
A STUDY OF SELECTED FLOTATION OF ANTIMONITE
AND ARSENOPYRITE
Huang Kaiguo, Wang Dlunzuo and Huang Qinping
(Central-South Institute of Mining and Metallurgy)
In this paper, three ways of selected flotation of antimonite and arsenopyrite were given, they are: (1) selected collectors (such as dibutyl dithiophosphate ammonium, diethyl dithiocarbamate sodium and diethyl aminoethyl dithiocarbonate sodium etc.) method, (2) flotation method in The alkaline results and the oxidation of the anti-fighting method The av. solution at differential pH values ​​were given and then, the thermodynamic calculation and diagram conformed to these experimental results. From this, the two types of double layer models and their determined potential ions of antimonite surface were determined and the flotation phenomena can be The study also showed that the main product of reaction between antimonite and xanth Athe may be adsorbed in antimony xanthate form, but present dixanthogen too; the main product of reaction on arsenopyrite may be dixanthogen and the adsorption sect of xanthate form was observed too.
Originally published in this article "Non-ferrous Metals (Quarterly)" 1985, No2, 22 ☺
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