CN112453419B - Method for growing copper nano material in feldspar crystal - Google Patents

Method for growing copper nano material in feldspar crystal Download PDF

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CN112453419B
CN112453419B CN202011210279.8A CN202011210279A CN112453419B CN 112453419 B CN112453419 B CN 112453419B CN 202011210279 A CN202011210279 A CN 202011210279A CN 112453419 B CN112453419 B CN 112453419B
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copper
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CN112453419A (en
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周青超
王成思
沈锡田
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West Yunnan University Of Applied Sciences
China University of Geosciences
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China University of Geosciences
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Abstract

The invention discloses a method for growing a copper nano material in a feldspar crystal, which introduces a copper element into the feldspar crystal by means of high-temperature diffusion, and separates the process of growing the copper nano material in the feldspar crystal into two stages of diffusion and nucleation growth in order to shorten the growth period of the copper nano material in the feldspar crystal. The diffusion process of copper from the diffusion raw material to feldspar crystals is accelerated in the diffusion stage by increasing the concentration of copper in the diffusion raw material. No diffusion raw material is added in the nucleation and growth stages, the temperature is further raised to accelerate the diffusion of copper ions in the feldspar crystal, and the growth process of copper nanoparticles is accelerated. The method can greatly shorten the growth period of the copper nano material in the feldspar crystal.

Description

Method for growing copper nano material in feldspar crystal
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a preparation method of feldspar crystals containing copper nano materials.
Background
Feldspar is an aluminosilicate mineral containing Na, K and Ca. The materials can be divided into different subspecies according to the types and contents of Na, K and Ca, such as albite, anorthite, plagioclase feldspar, microcline feldspar, orthoclase, permeance feldspar, etc. Among these feldspar subspecies, the superior one can be used as a gem material. In the naturally produced transparent plagioclase feldspar crystals, a small part of the plausible crystals (usually red, green and champagne) have high purity and beautiful color, and the market price of the crystals is very high after the crystals are cut and ground into precious stones. In the naturally produced transparent feldspar crystals, a great part of the crystals have high purity, but no beautiful color is required.
Researchers have confirmed through long-term studies that the color of natural plagioclase feldspar crystals originates from the copper nanomaterial inside the crystals. Due to the local surface plasmon resonance effect of the copper nano material, absorption of different wave bands in visible light is caused, and colors which are finally seen by human eyes are generated. Based on the above, researchers adopt the traditional high-temperature diffusion treatment method to treat the colorless feldspar crystal, and bury the colorless feldspar crystal in a corundum crucible containing diffusion raw materials (zirconia and copper powder), wherein the mass percent of the copper powder is 1%. And then the feldspar crystal is treated at 1170 ℃ for 160h, and part of the obtained feldspar crystal is changed into red, but the treatment method has long period and high cost, is not suitable for large-scale treatment and limits the application of the feldspar crystal in gem materials. In addition, the transparent optical material containing the copper nano material has good nonlinear optical properties and also has high application value in photoelectric materials.
The invention discloses a method for growing a copper nano material in a feldspar crystal, which introduces a copper element into the feldspar crystal by means of high-temperature diffusion, and separates the process of growing the copper nano material in the feldspar crystal into two stages of diffusion and nucleation growth in order to shorten the growth period of the copper nano material in the feldspar crystal. The diffusion process of copper from the diffusion raw material to feldspar crystals is accelerated in the diffusion stage by increasing the concentration of copper in the diffusion raw material. No diffusion raw material is added in the nucleation and growth stages, the temperature is further raised to accelerate the diffusion of copper ions in the feldspar crystal, and the growth process of the copper nano material is accelerated. The method can greatly shorten the growth period of the copper nano material in the feldspar crystal.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art and provides a method for growing a copper nano material in feldspar crystals. According to an embodiment of the invention, the method comprises:
1) transferring the prepared diffusion raw material into a crucible A, and embedding feldspar crystals into the diffusion raw material;
2) placing the crucible A filled with the diffusion raw material and the feldspar crystals into heating equipment for high-temperature diffusion treatment, taking out the crucible A after the high-temperature diffusion treatment, and placing the crucible A in air for rapid cooling;
3) transferring the feldspar crystal obtained by the high-temperature diffusion treatment in the step 2) into a crucible B, then putting the crucible B into heating equipment for secondary high-temperature heat treatment, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the feldspar crystal to finally obtain the feldspar crystal containing the copper nano material.
According to an embodiment of the present invention, the diffusion raw material includes a substance X containing a copper element, and an oxide Y;
the substance X containing the copper element is selected from one or more of copper, copper-tin alloy, copper oxide, copper sulfide and copper halide;
the oxide Y is selected from one or more of zirconium oxide, silicon oxide, calcium oxide, zinc oxide and magnesium oxide.
According to the embodiment of the invention, the mass ratio of the amount of the substance X containing the copper element to the feldspar crystal is (0.00078-0.0156mol):1g, and the mass ratio of the oxide Y to the feldspar crystal is (0.5-10): 1.
According to the embodiment of the invention, the temperature range of the high-temperature diffusion treatment in the step 2) is 800-1500 ℃.
According to the embodiment of the invention, the time of the high-temperature diffusion treatment in the step 2) is 1-24 h.
According to the embodiment of the invention, the temperature range of the secondary high temperature heat treatment in the step 3) is 900-1600 ℃.
According to the embodiment of the invention, the time of the secondary high-temperature heat treatment in the step 3) is 8-48 h.
According to an embodiment of the present invention, the temperature of the secondary high temperature heat treatment in step 3) is 50 to 200 ℃ higher than the temperature of the high temperature diffusion treatment in step 2).
According to an embodiment of the present invention, the feldspar crystal is selected from one of albite crystal, anorthite crystal, andesine crystal, labradorite crystal, pefeldspar crystal, anorthite crystal.
The invention has the following beneficial effects:
(1) because the copper diffusion stage is separated from the nucleation growth stage of the copper nano material, high-concentration copper can be introduced into the diffusion raw material in the high-temperature diffusion treatment stage, so that the diffusion transfer rate of the precursor copper from the diffusion raw material to the feldspar crystal can be greatly improved, copper with different concentrations can be introduced into the feldspar crystal according to the adjustment of the diffusion time, and the residual copper in the diffusion raw material cannot be brought into the next stage;
(2) after the feldspar crystal is subjected to the high-temperature diffusion treatment, the defects are introduced into the feldspar crystal in the process of rapid cooling in the air, and the defects are favorable for forming copper nanometer material crystal nuclei during secondary high-temperature heat treatment;
(3) the temperature difference is designed between the high-temperature diffusion treatment stage and the nucleation growth stage, the damage to the surface of the feldspar crystal caused by diffusion treatment can be reduced by reducing the temperature of the high-temperature diffusion treatment, the temperature of the secondary high-temperature heat treatment in the nucleation growth stage is increased, the diffusion of copper in the feldspar crystal can be accelerated, and the growth of a copper nano material is accelerated.
Drawings
FIG. 1 is a flow chart of growing copper nano-materials in feldspar crystals;
FIG. 2 is the appearance of an anorthite crystal before high temperature diffusion treatment in example 1 of the present invention;
FIG. 3 is an EDXRF spectrum of high temperature diffusion treated prearranged crystals in example 1 of the present invention;
FIG. 4 shows the appearance of an anorthite crystal obtained by high-temperature diffusion treatment and rapid cooling in example 1 of the present invention;
FIG. 5 is an EDXRF spectrum of the anorthite crystal containing copper nanomaterial obtained after high temperature diffusion treatment in example 1 of the present invention;
FIG. 6 shows the appearance of an anorthite crystal obtained by simple cutting and grinding after the secondary high-temperature heat treatment in example 2 of the present invention;
fig. 7 is a TEM photograph of the labrador crystal containing the copper nanomaterial obtained after the secondary high temperature heat treatment in example 2 of the present invention;
fig. 8 is the polished appearance of the labrador crystal obtained by high-temperature diffusion treatment and rapid cooling in example 3 of the present invention;
fig. 9 is a transmittance spectrum measured after polishing of an anorthite crystal obtained by high-temperature diffusion treatment and rapid cooling in example 3 of the present invention;
fig. 10 is an ultraviolet-visible absorption spectrum of the anorthite crystal obtained after the secondary high-temperature heat treatment in example 3 of the present invention after polishing.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following describes a method for growing copper nano-materials in feldspar crystals in detail, which is disclosed in the present invention, with reference to the accompanying drawings.
Fig. 1 is a flow chart of growing copper nano-material in feldspar crystal according to the present invention, as shown in fig. 1, 101 is a crucible a for holding diffusion raw material and feldspar crystal, and the crucible selected by the present invention is a corundum crucible with the highest processing temperature up to 1700 ℃ according to the diffusion processing temperature interval required for the feldspar crystal. 102 are pre-prepared and uniformly mixed diffusion materials, and diffusion materials of different components are generally guaranteed to have similar meshes so as to guarantee the mixing quality. 103 are feldspar crystals embedded in the diffusion material.
The invention discloses a method for growing a copper nano material in feldspar crystals. According to an embodiment of the invention, the method comprises:
1) transferring the prepared diffusion raw material into a crucible A, and embedding feldspar crystals into the diffusion raw material;
2) placing the crucible A filled with the diffusion raw material and the feldspar crystals into heating equipment for high-temperature diffusion treatment, taking out the crucible A after the high-temperature diffusion treatment, and placing the crucible A in air for rapid cooling;
3) transferring the feldspar crystal obtained by the high-temperature diffusion treatment in the step 2) into a crucible B, as shown by 104 in figure 1, putting the crucible B into heating equipment for secondary high-temperature heat treatment, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the feldspar crystal containing the copper nano material.
According to the embodiment of the invention, in the step 1), the mass of each component in the diffusion raw material is calculated according to the mass of the feldspar crystal to be processed, wherein the total amount of substances of the substance X which is required to be weighed and corresponds to the copper element in each 1g of the feldspar crystal is 0.00078-0.0156mol, the mass of the corresponding oxide Y is 0.5-10g in each 1g of the feldspar crystal, the oxide Y is an oxide with a high melting point, the melting point is more than 1700 ℃, and the addition of the oxide with the high melting point can ensure that the components of the diffusion raw material are always kept in a solid state in the high-temperature processing process, so that the surface damage of the feldspar crystal in the high-temperature diffusion processing process is reduced to a certain extent; on the other hand, the addition of the refractory oxide serves to dilute the copper element-containing substance X, and the desired molarity of the copper element-containing substance X is obtained by adjusting the mass of the refractory oxide. According to the ICP-MS test, 1g of the natural copper-containing nanoparticle feldspar crystal contained about 500ppmw of copper, i.e., the molar mass concentration of copper in the natural copper-containing nanoparticle feldspar crystal was 0.0000078 mol/g. According to the embodiment of the invention, in the step 1), the mass molar concentration of the copper element-containing substance X in the diffusion raw material to the refractory oxide component is 0.00078-0.0156mol/g, which is 100-2000 times of the mass molar concentration of copper in the natural copper-containing nanoparticle feldspar crystal. The mass molarity of copper ions in the diffusion raw material is far higher than that of the natural feldspar crystal containing the copper nanoparticles, so that the copper diffused into the feldspar crystal can form a nano material. Because the molarity of the copper ions in the diffusion raw material is far higher than that of the feldspar crystal, a large diffusion driving force (ion concentration difference) is formed, the process that the copper ions enter the feldspar crystal from the diffusion raw material is correspondingly accelerated, and copper with enough concentration is diffused in the feldspar crystal. According to an embodiment of the invention, in the step 1), the substance X containing copper element is selected from one or more of copper, copper-tin alloy, copper oxide, copper sulfide and copper halide, and the proportion of each substance containing copper element can be adjusted between 0% and 100% according to actual needs. According to an embodiment of the invention, the refractory oxide is selected from one or more of zirconia, silica, calcia, zinc oxide, magnesia. According to an embodiment of the present invention, in step 1), in order to ensure that copper ions can diffuse into the feldspar crystals from multiple directions, the feldspar crystals are completely embedded in the diffusion raw material.
According to an embodiment of the invention, in step 1), the feldspar crystals compriseAlbite crystal, anorthite crystal, melilite crystal, labradorite crystal, pefeldspar crystal and anorthite crystal. When Ab represents albite and An represents anorthite, the solid solution formed by albite and anorthite has albite crystal (Ab90-100%An0-10%) Austenite crystal (Ab)70-90%An10-30%) Middle feldspar crystal (Ab)50-70%An30-50%) Anorthite crystal (Ab)30-50%An50-70%) Pegyanite crystal (Ab)10-30%An70-90%) Anorthite crystal (Ab)0-10%An90-100%）。
According to the embodiment of the invention, in the step 2), the temperature range of the high-temperature diffusion treatment is 800-. The temperature of the high-temperature diffusion treatment depends on the type of the selected feldspar crystal, different feldspar crystals have different solidus temperatures, and the temperature of the high-temperature diffusion treatment cannot be higher than the solidus temperature of the selected feldspar crystal. According to the embodiment of the invention, in the step 2), the time of the high-temperature diffusion treatment is 1-24 h. With the increase of the high-temperature diffusion treatment time, the concentration of copper diffused into the feldspar crystal is increased. According to the embodiment of the invention, in the step 2), after the high-temperature diffusion treatment is finished, the feldspar crystal is directly taken out and rapidly cooled in the air, and the defects are generated in the feldspar crystal through the quenching effect, so that the nucleation and the growth of the copper nano material in the subsequent step are facilitated.
According to the embodiment of the invention, in the step 3), the temperature range of the secondary high temperature heat treatment is 900-. The temperature of the secondary high-temperature heat treatment depends on the type of the selected feldspar crystal, different feldspar crystals have different solidus temperatures, and the temperature of the secondary high-temperature heat treatment cannot be higher than the solidus temperature of the selected feldspar crystal. According to the embodiment of the invention, in the step 3), the time of the secondary high temperature heat treatment is 8-48h, and the size of the copper nano material grown in the feldspar crystal is increased along with the increase of the time of the secondary high temperature heat treatment. According to the embodiment of the invention, in the step 3), the temperature of the secondary high-temperature heat treatment is 50-200 ℃ higher than that of the high-temperature diffusion treatment in the step 2), so that the diffusion of copper in feldspar crystals can be accelerated, and the growth of copper nano materials can be accelerated. Meanwhile, the temperature of the high-temperature diffusion treatment can be relatively reduced, so that the surface damage of the feldspar crystal in the high-temperature diffusion process is reduced.
According to an embodiment of the present invention, in step 3), the secondary high temperature heat treatment may be selectively performed in an air atmosphere, an inert gas atmosphere, and a weakly reducing atmosphere. The copper nano material can grow in the feldspar crystal by high-temperature secondary high-temperature heat treatment under three atmosphere conditions. According to an embodiment of the present invention, in step 3), when the secondary high temperature heat treatment is performed under an inert gas atmosphere or a weakly reducing atmosphere, the purity of the copper nanomaterial grown in the feldspar crystal may be improved to some extent. In the present invention, unless otherwise specified, the secondary high-temperature heat treatment is carried out in an air atmosphere.
The present invention is described below by way of specific embodiments, it should be noted that the following specific embodiments are for illustrative purposes only and do not limit the scope of the present invention in any way, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also regarded as the protection scope of the present invention. In addition, unless otherwise specified, methods in which conditions or steps are not specifically recited are all conventional methods, and reagents and materials used therefor are commercially available.
Example 1
(1) Weighing 0.647g of zirconium oxide powder and 0.361g of cuprous oxide powder as diffusion raw materials, uniformly mixing in an agate mortar, and pouring into a corundum crucible A; embedding the labrador crystal (0.647 g) in a diffusion raw material, wherein the appearance of the labrador crystal before high-temperature diffusion treatment is shown in figure 2 and is colorless and transparent, and the EDXRF (electron-ray diffraction) spectrum of the tested labrador crystal before high-temperature diffusion treatment is shown in figure 3, so that no signal of copper element is detected;
(2) and (3) putting the crucible A filled with the diffusion raw materials and the labrador crystal into a high-temperature tube furnace, heating to 1100 ℃, and performing high-temperature diffusion treatment for 8 hours. After the high-temperature diffusion treatment is finished, taking out the crystal, placing the crystal in the air for rapid cooling, wherein the appearance of the anorthite crystal obtained after cooling is shown in figure 3, the surface of the anorthite crystal is grey black, and the interior of the crystal is transparent;
(3) and (3) transferring the labrador crystal obtained by the high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1200 ℃ for 8h, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the labrador crystal, wherein the finally obtained labrador crystal is red. The EDXRF pattern of the anorthite crystal after the secondary high-temperature heat treatment is shown in figure 5, and a strong signal of copper element can be seen.
Example 2
(1) Weighing diffusion raw materials of 0.768g of zirconia powder and 0.953g of copper oxide powder, putting the diffusion raw materials in an agate mortar, uniformly mixing, and pouring the mixture into a corundum crucible A; then embedding colorless and transparent labrador crystals (0.768 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw materials and the labrador crystal into a high-temperature tube furnace, heating to 1150 ℃, and performing high-temperature diffusion treatment for 4 hours. After the high-temperature diffusion treatment is finished, taking out the product, placing the product in the air, and rapidly cooling the product to obtain a blackish gray crystal surface;
(3) and (3) transferring the labrador crystal obtained by the high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1200 ℃ for 10h, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the labrador crystal, wherein the finally obtained labrador crystal is light red. And (3) simply cutting and grinding the anorthite crystal obtained by the secondary high-temperature heat treatment to obtain a polished surface, wherein the appearance is shown in figure 6, and the polished crystal is transparent and dark red. In order to verify the morphology of the copper nanoparticles, a slice for TEM observation was prepared by FIB cutting, and fig. 7 shows the distribution of the copper nanoparticles in the labrador crystal as seen by TEM, and the particle size of the obtained copper nanoparticles was about 10 nm.
Example 3
(1) Weighing 1.78g of silicon oxide powder and 0.444g of copper powder as diffusion raw materials, placing the raw materials in an agate mortar, uniformly mixing, and then pouring the mixture into a corundum crucible A; then embedding colorless and transparent labrador crystals (0.890 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw materials and the labrador crystals into a high-temperature tube furnace, heating to 1050 ℃, and performing high-temperature diffusion treatment for 12 hours. And after the high-temperature diffusion treatment is finished, taking out the product, placing the product in the air for rapid cooling, and cooling to obtain a blackish gray crystal surface. Cutting, grinding and polishing the anorthite crystal obtained by cooling to obtain a parallel surface with the appearance shown in figure 8, wherein the interior of the crystal is colorless and transparent after polishing, and the light transmittance is tested, and the maximum light transmittance is close to 80%;
(3) and (3) transferring the feldspar crystals subjected to high-temperature diffusion treatment and cutting and grinding in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment, wherein the temperature of the secondary high-temperature heat treatment is 1200 ℃, the treatment time is 8 hours, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the feldspar crystals, wherein the finally obtained feldspar crystals are red. Fig. 10 shows the ultraviolet-visible absorption spectrum of the labrador crystal after the secondary high-temperature heat treatment, which shows that the characteristic absorption peak of the copper nanoparticles is near 580 nm.
Example 4
(1) 1.346g of calcium oxide powder and 0.167g of copper oxide which are used as diffusion raw materials are weighed, placed in an agate mortar and evenly mixed, and then poured into a corundum crucible A; then embedding transparent feldspar crystals (0.673 g) in the diffusion raw materials;
(2) and (3) putting the crucible A filled with the diffusion raw material and the feldspar crystal into a high-temperature tube furnace, heating to 1000 ℃, and performing high-temperature diffusion treatment for 24 hours. After the high-temperature diffusion treatment is finished, taking out the feldspar and placing the feldspar in the air for rapid cooling, wherein the surface of the feldspar crystal obtained after cooling is gray black;
(3) and (3) transferring the medium feldspar crystal subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1100 ℃ for 12h, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the medium feldspar crystal to obtain the red medium feldspar crystal. After the copper nano particles are cut, ground and polished, the ultraviolet visible absorption spectrum is tested, and the characteristic absorption peak of the copper nano particles can be seen near 580 nm.
Example 5
(1) Weighing 1.416g of zinc oxide powder and 0.220g of cuprous sulfide as diffusion raw materials, uniformly mixing in an agate mortar, and pouring into a corundum crucible A; then embedding the anorthite crystal (0.994 g) in a diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw material and the anorthite crystal into a high-temperature tube furnace, heating to 1000 ℃, and performing high-temperature diffusion treatment for 14 hours. After the high-temperature diffusion treatment is finished, taking out the austenitic feldspar and placing the austenitic feldspar in the air for quick cooling, wherein the surface of the austenitic feldspar obtained after cooling is gray black;
(3) transferring the anorthite crystal subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1050 ℃ for 32h, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the anorthite crystal, wherein the obtained anorthite crystal is light red.
Example 6
(1) Weighing 0.863g of diffusion raw material magnesium oxide powder and 0.483g of copper sulfide, putting the materials into an agate mortar, uniformly mixing, and then pouring the mixture into a corundum crucible A; then embedding albite crystals (0.863 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw material and the albite crystal into a high-temperature tube furnace, heating to 900 ℃, and performing high-temperature diffusion treatment for 18 hours. After the high-temperature diffusion treatment is finished, taking out the albite crystal, placing the albite crystal in the air, and quickly cooling the albite crystal to obtain a blackish grey crystal;
(3) and (3) transferring the albite crystal subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1050 ℃ for 16h, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the crystal, wherein the obtained albite crystal is light red. After the copper nano particles are cut, ground and polished, the ultraviolet visible absorption spectrum is tested, and the characteristic absorption peak of the copper nano particles can be seen near 580 nm.
Example 7
(1) 1.776g of zirconium oxide powder serving as a diffusion raw material and 0.300g of copper-tin alloy (Cu 50%) powder are weighed, placed in an agate mortar and mixed uniformly, and then poured into a corundum crucible A; then embedding the petalite crystal (0.592 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw material and the petalite crystal into a high-temperature tube furnace, heating to 1300 ℃, and performing high-temperature diffusion treatment for 8 hours. After the high-temperature diffusion treatment is finished, taking out the product, placing the product in the air, and quickly cooling the product to obtain a peyronite crystal with a grayish black surface;
(3) and (3) transferring the feldspar crystals subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1400 ℃ for 8h, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the feldspar crystals, wherein the finally obtained feldspar crystals are light red.
Example 8
(1) Weighing 0.869g of zirconium oxide powder and 1.952g of cuprous iodide which are diffusion raw materials, placing the zirconium oxide powder and the cuprous iodide in an agate mortar, uniformly mixing, and pouring the mixture into a corundum crucible A; then embedding anorthite crystals (0.869 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw materials and the anorthite crystals into a high-temperature tube furnace, heating to 1400 ℃, and performing high-temperature diffusion treatment for 10 hours. After the high-temperature diffusion treatment is finished, taking out the anorthite crystal, placing the anorthite crystal in the air, and quickly cooling the anorthite crystal to obtain a gray black crystal surface;
(3) and (3) transferring the anorthite crystal subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace, and carrying out secondary high-temperature heat treatment under a weak reducing atmosphere (95% nitrogen and 5% hydrogen), wherein the temperature of the secondary high-temperature heat treatment is 1500 ℃, the treatment time is 24 hours, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the anorthite crystal, wherein the anorthite crystal is finally obtained in a light red color.
Example 9
(1) Weighing 1.561g of calcium oxide powder and 0.935g of copper powder which are diffusion raw materials, placing the materials in an agate mortar, uniformly mixing the materials, and pouring the mixture into a corundum crucible A; then embedding the feldspar crystal (1.561 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw material and the feldspar crystal into a high-temperature tube furnace, heating to 1000 ℃, and performing high-temperature diffusion treatment for 3 hours. After the high-temperature diffusion treatment is finished, taking out the feldspar and placing the feldspar in the air for rapid cooling, wherein the surface of the feldspar crystal obtained after cooling is gray black;
(3) and (3) transferring the medium feldspar crystals subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace to perform secondary high-temperature heat treatment in an argon atmosphere, wherein the temperature of the secondary high-temperature heat treatment is 1150 ℃, the treatment time is 6 hours, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the medium feldspar crystals to obtain the medium feldspar crystals in red. After the copper nano particles are cut, ground and polished, the ultraviolet visible absorption spectrum is tested, and the characteristic absorption peak of the copper nano particles can be seen near 580 nm.
Example 10
(1) Weighing 1.231g of calcium oxide powder, 0.399g of copper powder and 0.799g of copper-tin alloy powder which are used as diffusion raw materials, placing the raw materials in an agate mortar, uniformly mixing, and then pouring the mixture into a corundum crucible A; then embedding feldspar crystals (1.231 g) in the diffusion raw material;
(2) and (3) putting the crucible A filled with the diffusion raw material and the feldspar crystal into a high-temperature tube furnace, heating to 1000 ℃, and performing high-temperature diffusion treatment for 6 hours. After the high-temperature diffusion treatment is finished, taking out the feldspar and placing the feldspar in the air for rapid cooling, wherein the surface of the feldspar crystal obtained after cooling is gray black;
(3) and (3) transferring the medium feldspar crystals subjected to high-temperature diffusion treatment in the step (2) into a corundum crucible B, then placing the crucible B into a high-temperature tube furnace for secondary high-temperature heat treatment at 1100 ℃ for 48 hours, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the medium feldspar crystals to obtain the medium feldspar crystals in red. After the copper nano particles are cut, ground and polished, the ultraviolet visible absorption spectrum is tested, and the characteristic absorption peak of the copper nano particles can be seen near 580 nm.

Claims (8)

1. A method for growing a copper nano material in feldspar crystals is characterized by comprising the following steps:
1) transferring the prepared diffusion raw material into a crucible A, and embedding feldspar crystals into the diffusion raw material;
the diffusion raw material comprises a substance X containing copper element and an oxide Y;
the substance X containing the copper element is selected from one or more of copper, copper-tin alloy, copper oxide, copper sulfide and copper halide;
the oxide Y is selected from one or more of zirconium oxide, silicon oxide, calcium oxide, zinc oxide and magnesium oxide;
the mass ratio of the amount of the substance X containing the copper element to the feldspar crystals is (0.00078-0.0156mol):1g, and the mass ratio of the oxide Y to the feldspar crystals is (0.5-10): 1;
2) placing the crucible A filled with the diffusion raw material and the feldspar crystals into heating equipment for high-temperature diffusion treatment, taking out the crucible A after the high-temperature diffusion treatment, and placing the crucible A in air for rapid cooling;
3) transferring the feldspar crystal obtained by the high-temperature diffusion treatment in the step 2) into a crucible B, then putting the crucible B into heating equipment for secondary high-temperature heat treatment, cooling to room temperature after the secondary high-temperature heat treatment is finished, and taking out the feldspar crystal to finally obtain the feldspar crystal containing the copper nano material.
2. The method as claimed in claim 1, wherein the temperature range of the high temperature diffusion treatment in step 2) is 800-1500 ℃.
3. The method according to claim 1, wherein the time of the high temperature diffusion treatment in step 2) is 1 to 24 hours.
4. The method as claimed in claim 1, wherein the temperature range of the secondary high temperature heat treatment in step 3) is 900-1600 ℃.
5. The method as claimed in claim 1, wherein the time of the secondary high temperature heat treatment in the step 3) is 8 to 48 hours.
6. The method according to claim 1, wherein the temperature of the secondary high temperature heat treatment in step 3) is 50 to 200 ℃ higher than the temperature of the high temperature diffusion treatment in step 2).
7. The method according to claim 1, wherein the feldspar crystal is selected from one of albite crystal, anorthite crystal, andesine crystal, labradorite crystal, pefeldspar crystal and anorthite crystal.
8. The feldspar crystal containing the copper nanomaterial prepared by the method according to any one of claims 1 to 7.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB687159A (en) * 1949-05-19 1953-02-11 Dentists Supply Co Improvements in or relating to the manufacture of artificial teeth
CN1390793A (en) * 2002-07-29 2003-01-15 李伟达 Process for preparing golden marble glass mosaic
CN1786297A (en) * 2004-12-10 2006-06-14 中国科学院理化技术研究所 Flux growing method of R2CaB10O19 monocrystal
CN105369352A (en) * 2015-09-17 2016-03-02 中国科学院上海光学精密机械研究所 Carbon-copper double-doped sapphire crystal and preparing method thereof
CN110105950A (en) * 2019-06-18 2019-08-09 湖北理工学院 A kind of natural albite luminescent material of doping with rare-earth ions and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB687159A (en) * 1949-05-19 1953-02-11 Dentists Supply Co Improvements in or relating to the manufacture of artificial teeth
CN1390793A (en) * 2002-07-29 2003-01-15 李伟达 Process for preparing golden marble glass mosaic
CN1786297A (en) * 2004-12-10 2006-06-14 中国科学院理化技术研究所 Flux growing method of R2CaB10O19 monocrystal
CN105369352A (en) * 2015-09-17 2016-03-02 中国科学院上海光学精密机械研究所 Carbon-copper double-doped sapphire crystal and preparing method thereof
CN110105950A (en) * 2019-06-18 2019-08-09 湖北理工学院 A kind of natural albite luminescent material of doping with rare-earth ions and its preparation method and application

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