AU2020100499A4 - Model afm probe for oxidized mineral collector, preparation method and application thereof - Google Patents

Model afm probe for oxidized mineral collector, preparation method and application thereof Download PDF

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AU2020100499A4
AU2020100499A4 AU2020100499A AU2020100499A AU2020100499A4 AU 2020100499 A4 AU2020100499 A4 AU 2020100499A4 AU 2020100499 A AU2020100499 A AU 2020100499A AU 2020100499 A AU2020100499 A AU 2020100499A AU 2020100499 A4 AU2020100499 A4 AU 2020100499A4
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group
probe
oxidized mineral
mineral collector
formula
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Jian Cao
Zhiyong Gao
haisheng HAN
Yuehua HU
Wei Sun
Mengjie TIAN
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Central South University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

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Abstract

The present invention belongs to the technical field of force measurement and reagent preparation, and particularly relates to model atomic force measurement (AFM) probe for an oxidized mineral collector. The AFM probe includes a probe with a surface compounded with an Au layer, and a modified oxidized mineral collector, where the oxidized mineral collector is a compound having the structural formula: Y-A (Formula 1); Y is a hydrophobic group, which is an aromatic group, an alkane group or an olefin group; A is an active group, which is a carboxylic acid or a hydroxamic acid; the modified oxidized mineral collector modifies Y with -SH and forms a coordination compound from A and an M metal ion; the modified oxidized mineral collector is anchored on the Au layer of the probe by the -SH therein. The present invention further discloses a preparation method and an application of the probe. The present invention fills in a gap of direct force measurement between an oxidized mineral collector and a mineral in the prior art. The present invention directly measures the force between the reagent and the mineral surface with an accurate measurement method. Pb2*-activated spodumene surface spodumene surface . jSpodumene110) in 10'MKCISoluion, PH 8.0 25 Souee10il M.~l~o~H. 25- b ~its 10- -5 0 5 10 i5 20 25 30 10 15 20 25 30 35 AdhesioN/Radius, F_/R (mN~m) AdhesionRadius .,R(mN/n)

Description

MODEL AFM PROBE FOR OXIDIZED MINERAL COLLECTOR, PREPARATION METHOD AND APPLICATION THEREOF
TECHNICAL FIELD
The present invention relates to the technical field of force measurement and reagent preparation, and in particular, to a method for measuring a force between flotation reagent and mineral surface by an atomic force microscope (AFM) and a method for preparing a reagent for force measurement.
BACKGROUND
The adsorption of organic molecules by inorganic materials has been widely used in environmental governance and mineral flotation, etc. Carbon nanotubes and activated carbon can efficiently adsorb organic pollutants such as o-chlorobenzoic acid and antibiotics in water. Flotation is an important method for enriching fine-grained valuable minerals. The selective adsorption of organic collectors on the surface of the target mineral can significantly improve the surface hydrophobicity of the target mineral, thereby separating the target mineral from the gangue mineral. In water polluted with organics, metal ions such as Pb2+ and Cu2+ are unavoidable. Compared with organic pollutants, metal ions can be preferentially adsorbed on the surface of the inorganic materials such as carbon nanotubes and activated carbon, which has a dual impact on the subsequent adsorption of organic materials. First, the hydrated layer of metal ions in the liquid phase will shield the hydrophobic sites of the inorganic materials and hinder the adsorption of the organic pollutants. Second, metal ions have a bridging effect, which will promote the adsorption of organic pollutants by the materials. In mineral flotation, metal ions, commonly used as activators, are usually artificially added to the ore slurry before the collectors to promote the adsorption of organic collectors on the surface of the target mineral. Recent studies have shown that metal ion-organic complexes prepared by mixing metal ions with the collectors in advance have a stronger adsorption capacity on the mineral surface.
Due to the special properties of the solid-liquid interface of the mineral and water phase, the reaction between the mineral surface and the reagent molecules is complex, and the direct observation of atomic microscopic phenomena is difficult. At present, there is a lack of direct i
2020100499 31 Mar 2020 characterization of the interaction strength between the reagent molecules and the mineral surface in the solution. Traditional measurement methods include adsorption test, zeta potential measurement, infrared (IR) spectrum and X-ray photoelectron spectroscopy (XPS) analysis. They can only indirectly infer the adsorption strength of organic molecules on the mineral surface by the adsorption capacity, and the shift of the zeta potential of the mineral surface, the IR spectrum characteristic peak, and the XPS binding energy of metal ions on the mineral surface. All these traditional methods have shortcomings of poor sensitivity and low accuracy. Currently, there is a demand to find a high-sensitivity measurement method to reflect the real adsorption environment of organic molecules on the mineral surface.
SUMMARY
In order to fill the gap of direct force measurement between a flotation reagent and a mineral surface in the prior art, a first objective of the present invention is to provide a model AFM probe (referred to as a to-be-measured probe herein) for an oxidized mineral collector. The probe aims to modify the to-be-measured oxidized collector and anchor it to the probe, so as to realize the direct AFM measurement.
A second objective of the present invention is to provide a method for preparing the to-be-measured probe.
A third objective of the present invention is to provide an application of the to-be-measured probe (that is, a method for measuring a force between an oxidized mineral collector and a mineral). This application aims to directly measure the force between the collector and the mineral by the to-be-measured probe through the AFM.
A model AFM probe for an oxidized mineral collector includes a probe with a surface treated by gold (Au) spraying, and a modified oxidized mineral collector, where the oxidized mineral collector is a compound having the structural formula:
Y-A
Formula 1
2020100499 31 Mar 2020 where Y is a hydrophobic group, which is an aromatic group, an alkane group or an olefin group; A is an active group, which is a carboxylic acid or a hydroxamic acid;
the modified oxidized mineral collector modifies Y with -SH and forms a coordination compound from A and an M metal ion;
the modified oxidized mineral collector is anchored on an Au layer of the probe by the -SH therein.
The present invention first creatively performs the modification treatment on the hydrophobic group and the active group of the oxidized mineral collector, and then anchors the modified oxidized mineral collector on the surface of the conventional probe by the modified groups thereof. In this way, the to-be-measured oxidized mineral collector is anchored on the probe, and the direct measurement of the force between the oxidized mineral collector and the mineral is achieved. According to the research of the present invention, it is found that the coordination modification of the active group of the oxidized mineral collector by the metal ion unexpectedly further improves the measurement effect and the measurement stability and accuracy.
In the present invention, the mercapto group (-SH) is introduced to the non-polar functional group (Y) of a measured reagent molecule (the oxidized mineral collector). Due to a strong interaction of the -SH with the precious metal gold (Au), the measured reagent molecule is fixed on an Au phase probe of an AFM by the -SH. The polar functional group (the active group) of the measured reagent molecule is exposed, facing away from the AFM probe and facing a liquid phase, while the non-polar functional group faces the probe and faces away from the liquid phase. The measured reagent molecule fixed on the AFM probe and the mineral surface modified with the M metal ion will produce a very weak inter-atomic force, which will cause a micro cantilever connected to the probe to deform. By detecting the deformation by a sensor, the force between the reagent molecule and the mineral surface is finally obtained. The present invention creatively coordinates the active group of the measured reagent with the M metal ion, which helps to further accurately measure the force between the reagent and the mineral. The AFM probe in the present invention directly measures the force between the reagent and the mineral, and obtains a more accurate and reliable result than a traditional detection method.
2020100499 31 Mar 2020
The technical solution of the present invention can be theoretically applied to any oxidized mineral collector.
Preferably, in Formula 1, Y is an aromatic group, which is a phenyl group or a heterocyclic aromatic group heterocyclized with at least one heteroatom of N, S, and O; the phenyl group and the heterocyclic aromatic group are allowed to have at least one substituent of a Ci-Ce alkane group, a Ci-Ce alkoxy group, a halogen and a nitro group.
Alternatively, Y is a long-chain alkane group or olefin group, and preferably a C12-C20 alkane group or a C12-C20 alkylene group.
Preferably, the oxidized mineral collector has the following structural formula:
O
Figure AU2020100499A4_D0001
Formula 1-A r2-cooh
Formula 1-B
R1 is a Ci-Ce alkane group, a Ci-Ce alkoxy group, a halogen or a nitro group;
R2 is a C12-C20 alkane group or a C12-C20 alkylene group having 1-3 double bonds; the oxidized mineral collector is a benzohydroxamic acid or an oleic acid.
Preferably, the oxidized mineral collector is a benzohydroxamic acid or an oleic acid.
The present invention modifies the hydrophobic group of the oxidized mineral collector with the -SH by a conventional method. Alternatively, the present invention uses a -SH-containing oxidized mineral collector, which is obtained by synthesizing a -SH-containing substrate on the hydrophobic group by a conventional method
Preferably, the M metal ion is at least one of a lead ion (Pb2+), a calcium ion (Ca2+) and an iron ion (Fe3+).
2020100499 31 Mar 2020
In the present invention, an existing method can be used to mix the active group of the oxidized mineral collector with the M metal ion. For example, the collector is immersed in a solution containing the M metal ion for complexing.
When the oxidized mineral collector is a compound of Formula 1-A, the oxidized mineral collector is modified by thiolating on a benzene ring of Formula 1-A and coordinating the hydroxamic acid with the M metal ion; the modified oxidized mineral collector has the following structural formula:
Figure AU2020100499A4_D0002
Ό' * ’ 2+ or 3+
Formula 1-A-1
When the oxidized mineral collector is a compound of Formula 1-B, the oxidized mineral collector is modified by thiolating on the R2 group of Formula 1-B and coordinating a carboxyl group with the M metal ion; the modified oxidized mineral collector has the following structural formula:
HS-R2-COO’-M
Formula 1-B-1
The present invention further provides a method for preparing the AFM probe for the oxidized mineral collector, including the following steps:
step (1): modifying the hydrophobic group of the oxidized mineral collector with the mercapto group to obtain a thiolated oxidized mineral collector having the following structural formula:
2020100499 31 Mar 2020
HS-Y-A
Formula 2 step (2): immersing the Au layer of the probe in a solution of the thiolated oxidized mineral collector, and anchoring on the probe by the force between the mercapto group and Au to obtain an Au-HS-Y-A probe; and step (3): coordinating and modifying with the M metal ion;
placing the Au-HS-Y-A probe treated in step (2) in a solution containing the M metal ion, and allowing the active group and the M metal ion to form a complex, and obtaining the model AFM probe for an oxidized mineral collector.
The technical solution of the present invention provides a method for anchoring the oxidized mineral collector on the AFM probe, so as to achieve the direct measurement of a force between the oxidized mineral collector and the mineral. In the technical solution of the present invention, an existing method is used to obtain a (-SH)-modified oxidized mineral collector in advance. Due to a special force between the -SH and the Au on the AFM probe, the oxidized mineral collector is anchored on the probe. The active group of the anchored oxidized mineral collector is creatively coordinated and modified with the M metal ion, thereby preparing the AFM probe. Studies have shown that the AFM probe prepared by the preparation method unexpectedly realizes the direct measurement of the force between the reagent and the mineral. In addition, the creative complexing of the active group helps to further improve the stability and accuracy of the measurement result.
The present invention can use an existing method to obtain the (-SH)-modified oxidized mineral collector.
Preferably, the thiolated oxidized mineral collector is a compound having the following structural formula:
O
HS
Figure AU2020100499A4_D0003
The compound of Formula 2-A is prepared as follows: performing an acylation reaction of a compound of Formula 3 to obtain an acylated product; performing an ammonolysis reaction with a compound of Formula 4 to obtain an ammonolysis product, and hydrolyzing the ammonolysis product;
2020100499 31 Mar 2020
Formula 2-A
Figure AU2020100499A4_D0004
Formula 3
Figure AU2020100499A4_D0005
Formula 4
Alternatively, the thiolated oxidized mineral collector is a compound having the structural formula as shown in Formula 2-B.
Preferably, in step (2), the immersion is not less than 6 h, preferably 8-12 h. After immersion, the probe is removed and washed with a solvent.
Preferably, in step (3), the immersion is not less than 5 min.
The present invention also provides a method for measuring the force between the oxidized mineral collector and the mineral, which uses the AFM probe to measure the force between the collector and the oxidized mineral.
Preferably, the oxidized mineral is previously modified with the M metal ion. For example, the oxidized mineral is previously immersed in a solution the M metal ion for modification.
In the present invention, the measurement condition is adjusted according to the actual condition of the to-be-measured oxidized mineral collector in the flotation experiments, so that the measurement condition matches an actual application scenario of the oxidized mineral collector.
2020100499 31 Mar 2020
Thus, the force between the oxidized mineral collector and the mineral in a real flotation process is reflected. In the method of the present invention, different measurement conditions are adopted, so as to provide a more suitable flotation collecting effect for the oxidized mineral collector according to the measurement data.
For example, the solution, where the oxidized mineral is immersed, is a pure aqueous solution or a salt solution (such as a solution of sodium chloride); the pH may be 1-14. The measured temperature can be room temperature.
The present invention provides a preferable measurement method, including the following technical solution:
A. synthesizing a reagent;
first introducing the mercapto group (-SH) into the non-polar functional group (Y) of the to-be-measured oxidized mineral collector by a chemical synthesis method, and then preparing a synthesized reagent (HS-Y-A) into a solution with a certain concentration;
B. modifying the AFM probe with the reagent;
modifying the AFM probe by the strong interaction between the -SH and the AFM probe; fixing a measured reagent molecule to an Au-coated AFM probe by the -SH, so that a polar functional group of the measured reagent molecule is exposed, facing away from the AFM probe and facing a liquid phase, while a non-polar functional group faces the probe and faces away from the liquid phase; obtaining an Au-HS-Y-A probe;
C. forming a metal ion I organic complex on the surface of the AFM probe;
immersing the AFM probe modified with the to-be-measured collector into an M metal ion solution, and removing it after a period of time;
D. modifying the mineral surface with the metal ion;
immersing the mineral surface in the metal ion solution, and removing it after a period of time; and
2020100499 31 Mar 2020
E. measuring the force;
using the AFM to measure the force on the surface of the mineral modified by the metal ion in the solution.
In the above technical solution, step B includes the following operations: immersing the AFM probe in a measured reagent I ethanol solution at a certain concentration for 10 h, then immersing the treated AFM probe into a pure ethanol solution for 10 min to wash the reagent molecule physically adsorbed on the probe surface, and finally obtain a monomolecular adsorption layer of the reagent on the surface of the AFM probe.
In the above technical solution, step C includes the following operations: immersing the AFM probe modified by the reagent molecule in an aqueous solution of the metal ion with a certain concentration for 10 min; then remove, and obtain a metal ion I organic complex formed on the surface of the AFM probe.
In the above technical solution, step D includes the following operations: immersing the mineral surface in an aqueous solution of the metal ion with a certain concentration for 10 min; then remove, and obtain a mineral surface modified with the metal ion.
In step E described in the above technical solution, the AFM measures the force between the reagent molecule and the mineral surface modified with the metal ion as well as the force between the metal ion I organic complex and the mineral surface in a pure aqueous solution or a salt solution with a certain concentration.
Beneficial Effects:
The present invention fills in a gap of direct force measurement between an oxidized mineral collector and a mineral in the prior art. The present invention creatively uses the -SH to anchor the to-be-measured collector on the probe, and further coordinates and modifies the active group of the anchored collector with the M metal ion, so that the measurement result is further improved.
BRIEF DESCRIPTION OF DRAWINGS
2020100499 31 Mar 2020
FIG. 1 is a schematic diagram of measuring the force between benzohydroxamic acid (BHA) and the Pb2+-modified spodumene surface by atomic force microscope (AFM) in 10'3 mol-L'1 KCI solution (a) and a schematic diagram of measuring the force between Pb-BHA complex and the spodumene surface by an AFM (b).
FIG. 2 is a histogram and a fitted normal distribution curve of the force between BHA and the Pb2+-modified spodumene surface measured by an AFM in 10'3 mol-L'1 KCI solution (a) and a histogram and a fitted normal distribution curve of the force between Pb-BHA complex and a spodumene surface by an AFM (b).
FIG. 3 is a relation diagram between spodumene flotation recovery and pH (a) and a relation diagram between spodumene flotation recovery and BHA dosage (b) under different reagent regimes.
FIG. 4 is a histogram and a fitted normal distribution curve of the force between oleic acid (OA) and the Ca2+-modified scheelite surface measured by an AFM in a 10'3 mol-L'1 KCI solution (a) and a histogram and a fitted normal distribution curve of a force between OA-Ca complex and the scheelite surface by an AFM (b).
DETAILED DESCRIPTION
The embodiments of the present invention are described in detail below. The present invention may be implemented in a variety of different ways defined and covered by the claims.
Embodiment 1
An atomic force microscope (AFM) is used to measure the force between benzohydroxamic acid (BHA) and the Pb2+-modified spodumene surface and the force between Pb-BHA complex and the spodumene surface. Specifically:
1. add a mercapto group (-SH) to modify the BHA ((CeH5) -CONHOH) to synthesize a new chemical substance (N-hydroxy-4-mercaptobenzamide, HS-(C6H4)-CONHOH, HMBA);
2. adhere the HMBA to an Au-coated AFM probe based on a strong interaction between the -SH and a precious metal gold (Au) to form an HMBA monomolecular adsorption layer on the io
AFM probe;
3. form a Pb2+-HMBA complex on a surface of the AFM probe;
4. determine the crystallographic orientations of the exposed surfaces by X-ray diffractometer (XRD) to find the (110) surface of spodumene crystal, and mount it inside the disc made of two-part epoxy resin, grind and polish, etc., to prepare the spodumene (110) surface sample with a roughness required for the force measurement of the AFM;
5. prepare the Pb2+-modified spodumene surface;
6. place the HMBA-modified AFM probe and the Pb2+-modified spodumene (110) surface sample in a 10'3 mol-L'1 potassium chloride (KCI) solution at pH 8 to measure the force between BHAand the Pb2+-modified spodumene (110) surface sample; place the AFM probe modified with Pb2+-HMBA complex and the spodumene (110) surface sample in a 10'3 mol-L'1 KCI solution at pH 8 to measure the force between the Pb-BHA complex and the spodumene (110) surface.
In step 1, the HMBA is synthesized as follows:
Figure AU2020100499A4_D0006
Figure AU2020100499A4_D0007
Figure AU2020100499A4_D0008
Figure AU2020100499A4_D0009
Figure AU2020100499A4_D0010
Figure AU2020100499A4_D0011
Figure AU2020100499A4_D0012
N-hydroxy-4mercapto benzamide preparation of substance 2: dissolve 4-mercaptobenzoic acid (500 mg, 3.24 mmol) in 10 ml dimethoxyethane, and add 0.75 ml N-methylmorpholine under stirring at room temperature; cool a reaction mixture to 0-5°C, and slowly add methyl chloroacetate (0.65 ml, 6.8 mmol); after the dropwise addition is completed, slowly return to room temperature, and stir for 3 h to obtain a solution containing the compound 2.
2020100499 31 Mar 2020 preparation of substance 3: directly add O-(2-methoxy-2-propyl) hydroxylamine
H2N.
( Ο O , 1.08 ml, 14.58 mmol) to a filtrate of the above reaction solution, and stir at room temperature for 2 h; concentrate the solvent under vacuum to obtain a solid crude product; dissolve the crude product in 10 ml water and 10 ml chloroform, separate an aqueous phase, adjust the pH to pH 8 with a KOH solution, and extract 3 times with 10 ml chloroform; combine an organic phase, and concentrate under vacuum to obtain the solid compound 3.
preparation of substance 4: dissolve the compound 3 in 10 ml methanol, add 20 ml 1 mmol sodium methoxide, and stir the reaction solution at room temperature for 5 h; after the reaction is completed, acidify to pH 5 with 10% acetic acid, and extract 4 times with 15 ml chloroform; dry the organic phase with a sulfuric acid, and concentrate under vacuum to obtain the compound 4.
preparation of substance 5: dissolve the above compound 4 in 5 ml methanol, and add 0.65 g amberlyst; stir the reaction solution at room temperature for 2 h, filter the resin off, concentrate a filtrate to obtain a crude product (HMBA), and recrystallize by ethanol.
In step 2, the AFM probe is modified as follows:
immerse the Au-coated AFM probe in 10'4 mol/L HMBA ethanol solution for 10 h, then immerse the AFM probe in the pure ethanol solution for 10 min, and wash the HMBA physically adsorbed on the probe surface.
In step 3, the Pb2+-HMBA complex forms on the AFM probe surface as follows:
immerse the HMBA-modified AFM probe in a 1.5 χ 10'4 mol-L’1 Pb2+ aqueous solution, and remove it after 10 min.
In step 5, the Pb2+-modified spodumene surface is prepared as follows:
immerse the spodumene (110) surface in 1.5 χ 10'4 mol-L'1 Pb2+aqueous solution, and remove it after 10 min.
In step 6, the AFM measures the force, as shown in FIG. 1.
The experimental results of the AFM force measurement are shown in FIG. 2. Each group of
2020100499 31 Mar 2020 force measurement experiments is performed for a total of 50 times, and the experimental results are obtained based on the 50 experiments, so the results have good repeatability. A fitted normal distribution curve indicates that the force between the BHAand the Pb2+-modified spodumene surface is 12.5 mN*rrr1 and the force between the Pb-BHA complex and the spodumene surface is 23.7 mN’nr1. This indicates that the Pb-BHA complex has a stronger adsorption capacity on the spodumene surface.
The experimental results of the spodumene flotation are shown in FIG. 3. Within the range of the pH and the BHA dosage studied, the Pb-BHA complex has a stronger ability to collect the spodumene than that of the BHA to collect the Pb2+-activated spodumene. This indicates that the Pb-BHA complex has a stronger adsorption capacity on the spodumene surface, which verifies the correctness of the AFM force measurement experiments.
Embodiment 2
Oleic acid (CH3(CH2)?CH = CH(CH2)?COOH, OA) is the most common collector for scheelite flotation. Its strong adsorption on the scheelite surface determines that it has a strong ability to collect scheelite. The process of OA adsorption to scheelite is often affected by a calcium ion (Ca2+) dissolved from a calcium-containing mineral, for example, scheelite and associated calcite. AFM is used to measure the force between OAand the Ca2+-modified scheelite surface and the force between OA / calcium complex (Ca2+-(16-MHA)) and the scheelite surface. Specifically:
1. directly purchase a 16-mercaptohexadecanoic acid (16-MHA, SH(CH2)i5COOH), where the 16-MHA has a similar structure to the OA, but unlike the OA, the 16-MHA adds a mercapto group (-SH) to a carbon chain and shortens the carbon chain by two methyl groups (CH3);
2. adhere the 16-MHA to an AFM Au phase probe based on a strong interaction between the -SH and a precious metal gold (Au) to form the 16-MHA monomolecular adsorption layer on the AFM probe;
3. form Ca2+-(16-MHA) complex on the AFM probe surface;
4. determine the crystallographic orientations of the exposed surfaces by X-ray diffractometer (XRD) to find the (112) surface of scheelite crystal, and mount it inside the disc made of two-part
2020100499 31 Mar 2020 epoxy resin, grind and polish, etc., to prepare the scheelite (112) surface sample with a roughness required for the force measurement of the AFM;
5. prepare the Ca2+-modified scheelite surface;
6. place the (16-MHA)-modified AFM probe and the Ca2+-modified scheelite (112) surface sample in 10'3 mol-L'1 KCI solution at pH 8 to measure the force between OAand the Ca2+-modified scheelite (112) surface sample; place the AFM probe modified with Ca2+-(16-MHA) complex and the scheelite (112) surface sample in 10'3 mol-L'1 KCI solution at pH 8 to measure the force between Ca2+-(16-MHA) complex and the scheelite (112) surface.
In step 2, the AFM probe is modified as follows:
immerse the Au-coated AFM probe in 2.5* 10'5 mol/L 16-MHA/ethanol solution for 10 h, then immerse the AFM probe in the pure ethanol solution for 10 min, and wash the 16-MHA physically adsorbed on the probe surface.
In step 3, the Ca2+-(16-MHA) complex forms on the AFM probe surface as follows:
immerse the (16-MHA)-modified AFM probe in 6 χ 10-4 mol-L'1 Ca2+ aqueous solution, and remove it after 10 min.
In step 5, the Ca2+-modified scheelite surface is prepared as follows:
immerse the scheelite (110) surface in 6 χ 104 mol-L'1 Ca2+ aqueous solution, and remove it after 10 min.
Each group of force measurement experiments are performed for a total of 50 times, and the experimental results are obtained based on the 50 experiments, so the results have good repeatability. A fitted normal distribution curve indicates that the force between OAand the Ca2+-modified scheelite surface is 33 mN*m'1 and the force between Ca2+-(16-MHA) complex and the scheelite surface is 65 mN*m'1. This indicates that the Ca2+-(16-MHA) complex has a stronger adsorption capacity on the scheelite surface.

Claims (5)

  1. What is claimed is:
    1. A model atomic force measurement (AFM) probe for an oxidized mineral collector, comprising a probe with a surface compounded with an Au layer, and a modified oxidized mineral collector, wherein the oxidized mineral collector is a compound having the structural formula:
    Y-A
    Formula 1 wherein Y is a hydrophobic group, which is an aromatic group, an alkane group or an olefin group; A is an active group, which is a carboxylic acid or a hydroxamic acid;
    the modified oxidized mineral collector modifies Y with -SH and forms a coordination compound from A and an M metal ion;
    the modified oxidized mineral collector is anchored on the Au layer of the probe by the -SH therein.
  2. 2. The model AFM probe for an oxidized mineral collector according to claim 1, wherein Y is an aromatic group, which is a phenyl group or a heterocyclic aromatic group heterocyclized with at least one heteroatom of N, S, and O; the phenyl group and the heterocyclic aromatic group are allowed to have at least one substituent of a Ci-Ce alkane group, a Ci-Ce alkoxy group, a halogen and a nitro group;
    alternatively, Y is a C12-C20 alkane group or a C12-C20 alkylene group;
    preferably, wherein the oxidized mineral collector has the following structural formula:
    Figure AU2020100499A4_C0001
    Formula 1-A r2-cooh
    2020100499 31 Mar 2020
    Formula 1-B
    R1 is a Ci-Ce alkane group, a Ci-Ce alkoxy group, a halogen or a nitro group;
    R2 is a C12-C20 alkane group or a C12-C20 alkylene group having 1-3 double bonds;
    the modified oxidized mineral collector is a compound formed by thiolating on the R1 group of Formula 1-A and coordinating the hydroxamic acid with the M metal ion, or thiolating on the R2 group of Formula 1-B and coordinating the hydroxamic acid with the M metal ion;
    preferably, the oxidized mineral collector is a benzohydroxamic acid or an oleic acid.
  3. 3. The model AFM probe for an oxidized mineral collector according to claim 1, wherein the M metal ion is at least one of a lead ion (Pb2+), a calcium ion (Ca2+) and an iron ion (Fe3+).
  4. 4. A preparation method of the model AFM probe for an oxidized mineral collector according to any one of claims 1-4, comprising the following steps:
    step (1): modifying the mercapto group on the hydrophobic group of the oxidized mineral collector to obtain a thiolated oxidized mineral collector having the following structural formula:
    HS-Y-A
    Formula 2 step (2): immersing the Au layer of the probe in a solution of the thiolated oxidized mineral collector, and anchoring on the probe by the force between the mercapto group and Au to obtain an Au-HS-Y-A probe; and step (3): coordinating and modifying with the M metal ion;
    placing the Au-HS-Y-A probe treated in step (2) in a solution containing the M metal ion, and allowing the active group to form a complex with the M metal ion, to obtain the AFM probe for the oxidized mineral collector;
    preferably, wherein the thiolated oxidized mineral collector is a compound having the following structural formula:
    ο
    Figure AU2020100499A4_C0002
    Formula 2-Α the compound of Formula 2-A is prepared as follows: performing an acylation reaction of a compound of Formula 3 to obtain an acylated product; performing an ammonolysis reaction with a compound of Formula 4 to obtain an ammonolysis product, and hydrolyzing the ammonolysis product;
    O
    HS-rr
    Figure AU2020100499A4_C0003
    OH ϊ£3
    Formula 3
    Formula 4;
    preferably, wherein in step (2), the immersion is not less than 6 h;
    preferably, wherein in step (3), the immersion is not less than 5 min.
  5. 5. A method for measuring a force between an oxidized mineral collector and a mineral, using the AFM probe according to any one of claims 1 -3 or preparing an AFM probe according to claim 4, and using an AFM to measure the force in the aqueous solution, preferably, wherein the oxidized mineral is previously modified with the M metal ion.
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