CN117304872A - Diamond abrasive material and preparation method and application thereof - Google Patents
Diamond abrasive material and preparation method and application thereof Download PDFInfo
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- CN117304872A CN117304872A CN202311248287.5A CN202311248287A CN117304872A CN 117304872 A CN117304872 A CN 117304872A CN 202311248287 A CN202311248287 A CN 202311248287A CN 117304872 A CN117304872 A CN 117304872A
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- 239000010432 diamond Substances 0.000 title claims abstract description 157
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 153
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003082 abrasive agent Substances 0.000 title description 6
- 238000005524 ceramic coating Methods 0.000 claims abstract description 41
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000004246 zinc acetate Substances 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 229910013553 LiNO Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 73
- 239000000499 gel Substances 0.000 description 36
- 238000003756 stirring Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000011240 wet gel Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002241 glass-ceramic Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- -1 silicon aluminum boron Chemical compound 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
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- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
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- 230000003685 thermal hair damage Effects 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
Abstract
The invention provides a diamond abrasive, a preparation method and application thereof, and relates to the technical field of materials. The diamond abrasive provided by the invention is diamond coated with a ceramic coating on the surface; the ceramic coating comprises the following components in percentage by mass: li (Li) 2 O 18％‑25％、ZnO 8％‑15％、Al 2 O 3 8％‑14％、TiO 2 1.5％‑2％、B 2 O 3 9% -10% and the balance of SiO 2 . The inventor researches find that the diamond abrasive has high thermal stability and excellent oxidation resistance. The preparation method of the diamond abrasive provided by the invention is simple and convenient, and the prepared diamond abrasive has high thermal stability and excellent oxidation resistance and can be used for preparing grinding tools.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a diamond abrasive, a preparation method and application thereof.
Background
In the superhard grinding tool, carbon atoms of diamond are connected into a compact structure through a covalent bond structure, so that the surface energy is high, good infiltration effect is difficult to form with a matrix material, mechanical bonding is mainly carried out between diamond abrasive particles and a bonding agent, and the bonding strength is low, so that the diamond abrasive particles are easy to fall off in the grinding process. Diamond is a hard brittle material, and during the production and processing process, some crystal defects or inclusion impurities exist on the surface and inside of diamond abrasive particles. The defects are more prominent in the low-grade abrasive, and the defects are easy to oxidize and break in the grinding process, so that the grinding function is lost.
In view of this, the present invention has been made.
Disclosure of Invention
A first object of the present invention is to provide a diamond abrasive to solve at least one of the above problems.
A second object of the present invention is to provide a method for producing the above diamond abrasive.
A third object of the present invention is to provide the use of the diamond abrasive as described above in the manufacture of an abrasive article.
In a first aspect, the present invention provides a diamond abrasive, which is diamond coated with a ceramic coating on the surface;
the ceramic coating comprises the following components in percentage by mass: li (Li) 2 O 18％-25％、ZnO 8％-15％、Al 2 O 3 8％-14％、TiO 2 1.5％-2％、B 2 O 3 9% -10% and the balance of SiO 2 。
As a further technical solution, the ceramic coating comprises, in mass percent: li (Li) 2 O17％、ZnO 8％、Al 2 O 3 13％、SiO 2 50％、TiO 2 2% and B 2 O 3 10％。
In a second aspect, the present invention provides a method for preparing the diamond abrasive, comprising the steps of:
a. purifying the surface of the diamond, and then soaking the diamond in a multi-element gel solution to obtain the diamond with gel attached to the surface;
b. c, sequentially drying, heating, oxidizing and sintering the diamond with gel attached to the surface obtained in the step a to prepare the diamond abrasive;
the solute of the polybasic gel solution comprises tetraethoxysilane and LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 O, zinc acetate and tetrabutyl titanate.
As a further technical scheme, the preparation method of the multi-component gel solution comprises the following steps:
mixing tetraethoxysilane, absolute ethyl alcohol and water to obtain a solution A; liNO is to be carried out 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 Mixing O, zinc acetate, tetrabutyl titanate and water to obtain a solution B; and then, dropwise adding the solution B into the solution A to obtain the multi-element gel solution.
As a further technical scheme, in the solution A, the mol ratio of the tetraethoxysilane to the absolute ethyl alcohol to the water is 1 (2-4) (0.5-1.5);
in the solution B, liNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 The total concentration of O, zinc acetate and tetrabutyl titanate is 0.6-1.0mol/L.
As a further technical scheme, the pH of the polybasic gel solution is 2-4.
As a further technical scheme, the drying temperature is 80-120 ℃ and the drying time is 0.5-2h;
as a further technical scheme, the temperature of the heating oxidation treatment is 783-823k, and the time is 1-2h;
preferably, the heating rate of the heating oxidation treatment is 1-10 ℃/min.
As a further technical scheme, the sintering temperature is 863-903K, and the sintering time is 1-3h.
In a third aspect, the present invention provides the use of the diamond abrasive described above in the manufacture of an abrasive article.
Compared with the prior art, the invention has the following beneficial effects:
the surface of the diamond abrasive material provided by the invention is coated with the specific ceramic coating, so that the diamond abrasive material can be protected from being oxidized in a high-temperature environment, and the service life of the abrasive tool is prolonged; the inventor researches find that the diamond abrasive has high thermal stability and excellent oxidation resistance.
The preparation method of the diamond abrasive provided by the invention is simple and convenient, and the prepared diamond abrasive has high thermal stability and excellent oxidation resistance and can be used for preparing grinding tools.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM micrograph of (a) uncoated diamond; (b) a ceramic-coated diamond; (c) a ceramic coating the diamond surface; (d) EDS spectra of the ceramic coating-coated diamond;
FIG. 2 shows TG-DTA curves of two different diamonds under flowing air (a 1) TG curves of ceramic coating coated diamonds; (b 1) a thermogravimetric curve of uncoated diamond; (a 2) a DTA curve of the ceramic coating-coated diamond; (b 2) DTA curve of uncoated diamond;
FIG. 3 is a Raman spectrum diagram: (a) uncoated diamond raman spectra without heat treatment; (b) 1000 ℃ treated uncoated diamond raman spectroscopy; (c) The ceramic coating treated at 1000 ℃ coats the Raman spectrum of the diamond;
FIG. 4 is a scanning electron microscope image of (a) uncoated diamond after heat treatment at 1000 ℃; (b) local amplification of uncoated diamond after 1000 ℃ heat treatment; (c) coating diamond with ceramic coating after sintering at 1000 ℃; (d) After 1000 ℃ heat treatment, the ceramic coating coats the diamond to locally amplify.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but it will be understood by those skilled in the art that the following embodiments and examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not specified, and the process is carried out according to conventional conditions or conditions suggested by manufacturers. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a diamond abrasive, which is diamond coated with a ceramic coating on the surface;
the ceramic coating comprises the following components in percentage by mass: li (Li) 2 O 18％-25％、ZnO 8％-15％、Al 2 O 3 8％-14％、TiO 2 1.5％-2％、B 2 O 3 9% -10% and the balance of SiO 2 。
The diamond abrasive material provided by the invention is coated with the specific ceramic coating, and the coating not only can improve the bonding strength between diamond and a matrix, but also can protect the diamond abrasive particles from being oxidized in a high-temperature environment and prolong the service life of the abrasive tool; the inventor researches find that the diamond abrasive has high thermal stability and excellent oxidation resistance.
In some preferred embodiments, the ceramic coating comprises, in mass percent: li (Li) 2 O17％、ZnO 8％、Al 2 O 3 13％、SiO 2 50％、TiO 2 2% and B 2 O 3 10％。
The effect of the prepared diamond abrasive is better through further optimization and adjustment of the ceramic coating composition.
In some preferred embodiments, the ceramic coating is sintered.
In a second aspect, the present invention provides a method for preparing the diamond abrasive, comprising the steps of:
a. purifying the diamond surface to remove impurities on the diamond surface, and soaking in a multi-gel solution to obtain diamond with gel attached to the surface, wherein the solute of the multi-gel solution comprises ethyl orthosilicate and LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 O, zinc acetate and tetrabutyl titanate;
b. drying the diamond with the gel attached to the surface obtained in the step a, and removing water and alcohol in the gel; then carrying out heating oxidation treatment, oxidizing an-OR group, and removing an-OH group in the structure; finally sintering to obtain the diamond abrasive with the surface coated with the ceramic coating.
The method is not particularly limited in the purification treatment mode, and impurities on the surface of the diamond can be removed.
The preparation method provided by the invention is simple and convenient, and the prepared diamond abrasive has high thermal stability and excellent oxidation resistance, and can be used for preparing the grinding tool.
In the multi-component gel solution, silicon aluminum boron element is a main component of ceramic; the lithium element is a component constituting lithium aluminum silicate crystals; hydrolysis of tetrabutyl titanate to produce TiO 2 ，TiO 2 As a nucleating agent, the crystallization of lithium aluminum silicate crystals can be more uniform, and the crystallization temperature is properly reduced; the addition of low-valence metal zinc and lithium can reduce the melting point of the ceramic and promote sintering.
In some preferred embodiments, the method of preparing the multi-gel solution comprises the steps of:
mixing tetraethoxysilane, absolute ethyl alcohol and water to obtain a solution A; liNO is to be carried out 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 Mixing O, zinc acetate, tetrabutyl titanate and water to obtain a solution B; and then, dropwise adding the solution B into the solution A to obtain the multi-element gel solution.
In some preferred embodiments, the method of preparing the multiple gel solution comprises the steps of:
1) Slowly adding deionized water into tetraethoxysilane, magnetically stirring in a constant-temperature water bath at 30-70 ℃ for 1-2h, adding absolute ethyl alcohol to assist dissolution during stirring, and fully dissolving to prepare solution A, wherein the solution A is uniform, transparent and stable.
2) Taking LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 O, zinc acetate, titaniumAdding tetrabutyl acid into deionized water sequentially for dissolution, magnetically stirring at room temperature for 1-2h, and fully mixing to form a mixed solution to prepare a solution B; wherein, boric acid is not only used as a boron source, but also has the functions of activation, coordination and buffering during glue mixing; tetrabutyl titanate needs absolute ethyl alcohol to be dissolved in advance, and the dosage of the absolute ethyl alcohol is as follows: 0.5L absolute ethyl alcohol is used for every 1mol of tetrabutyl titanate; the tetrabutyl titanate drop rate is preferably one drop every 30 s.
3) Slowly dripping the solution B into the solution A under the condition of constant-temperature water bath at 70 ℃, and dripping HNO in the process 3 The pH value of the reaction system is regulated to 2-4 by the solution, and the solution is stirred and fully mixed to prepare the polynary sol C solution.
In some preferred embodiments, the molar ratio of ethyl orthosilicate, absolute ethanol, and water in the liquid a may be, for example, but not limited to, 1:2:1.5, 1:3:1, or 1:4:0.5;
in the solution B, liNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 The total concentration of O, zinc acetate and tetrabutyl titanate is 0.6 to 1.0mol/L, preferably 0.8mol/L.
In some preferred embodiments, the pH of the multi-gel solution is from 2 to 4.
When the pH value of the multi-component gel solution is too small, the hydrolysis speed is high, the polycondensation speed is low, the hydrolysis is relatively complete, the chain structure of a sol system is complete, and the system is relatively stable; when the pH of the sol system is larger and the system is slightly acidic, the hydrolysis speed is slower, the polycondensation speed is faster, a large amount of gel is formed in the system, and the polymer is more, so that the system is unstable.
The inventor researches and discovers that. The pH of the multi-component gel solution is preferably 2-4, and under such conditions, the gel can be smoothly carried out, and the generation of suspended matters and the agglomeration of particles can be prevented. If the system is too acidic, ammonia water can be added to adjust the proper pH.
The ceramic coating prepared by the method has better effect through further optimizing and adjusting the preparation and components of the multi-component gel solution.
In some preferred embodiments, the temperature of the drying may be, for example, but not limited to, 80 ℃, 90 ℃, 100 ℃, 110 ℃, or 120 ℃, and the time of the drying may be, for example, but not limited to, 0.5h, 1h, 1.5h, or 2h.
In some preferred embodiments, the temperature of the thermal oxidation treatment may be, for example, but not limited to 783k, 793k, 803k, 813k, or 823k, and the time may be, for example, but not limited to 1h, 1.5h, or 2h;
preferably, the heating rate of the thermal oxidation treatment may be, for example, but not limited to, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min. In order to sufficiently dehydrate and oxidize the multi-element gel solution and release the generated gas, the temperature rising rate cannot be too fast, and is not more than 10 ℃/min.
In some preferred embodiments, the sintering temperature may be, for example, but not limited to 863K, 873K, 883K, 893K, or 903K, and the time may be, for example, but not limited to 1h, 2h, or 3h.
In a third aspect, the present invention provides the use of the diamond abrasive described above in the manufacture of an abrasive article.
The diamond abrasive provided by the invention has high thermal stability and excellent oxidation resistance, and can be used for preparing grinding tools.
The invention is further illustrated by the following specific examples and comparative examples, however, it should be understood that these examples are for the purpose of illustration only in greater detail and should not be construed as limiting the invention in any way.
The water used in the examples below was deionized water.
Example 1
A diamond abrasive is diamond coated with ceramic coating on the surface. Wherein the ceramic coating comprises the following components in percentage by mass:
Li 2 O17％、ZnO8％、Al 2 O 3 13％、SiO 2 50％、TiO 2 2% and B 2 O 3 10％。
The preparation method comprises the following steps:
slowly adding deionized water into tetraethoxysilane, stirring at a constant temperature of 30 ℃ for 2 hours, and adding absolute ethyl alcohol to assist dissolution during stirring to fully dissolve the tetraethoxysilane to prepare solution A;
taking analytically pure LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 O, zinc acetate and tetrabutyl titanate are sequentially added into deionized water for dissolution, and are fully mixed under magnetic stirring for 1h at room temperature to form a mixed solution to prepare a solution B;
slowly dripping the solution B into the solution A under the condition of stirring for 1h at the constant temperature of 70 ℃, and dripping HNO in the process 3 The pH value of the reaction system is regulated to 2 by the solution (1 vol%) to prepare a multiple sol C solution;
the diamond is purified and then soaked in the multi-element gel C liquid to obtain the diamond with wet gel attached to the surface;
drying diamond with wet gel attached on the surface at 80 ℃ for 2 hours, heating to 803K (heating rate is 5 ℃/min) in a muffle furnace for 2 hours, sintering for 2 hours at 883K, and cooling to obtain the diamond.
Comparative example 1
Diamond differs from example 1 in that the ceramic coating was not applied.
Test example 1
This test example was studied using the diamond abrasive provided in example 1 (denoted as coated diamond) and the diamond provided in comparative example 1 (denoted as uncoated diamond) as samples.
To observe the surface state of the diamond abrasive, SEM micrographs of uncoated and coated diamond are shown in fig. 1. As shown in fig. 1 (a), the uncoated diamond surface was flat and smooth. Fig. 1 (b) shows a coated diamond. Fig. 1 (c) is a partial enlarged view of fig. 1 (b), and a ceramic coating is coated on the diamond surface. To clarify the microstructure and elemental uniformity of the ceramic coating. As is clear from the spectroscopic analysis of the region (C) in fig. 1 (d) in fig. 1, the thin film coating layer on the diamond surface is composed of C, O, B, si, al, zn, ti and Li element, the C element is derived from diamond, and the Li element is not shown due to the atomic number being too small. As can be seen from the element map of the diamond thin film coating in FIG. 1 (d), the elements such as Si, O, al, etc. are uniformly distributed in the glass ceramic. The B element is mainly distributed around the diamond particles, and researchers have found that in the ceramic bond diamond composite material, B can segregate or diffuse into the diamond particles at the interface of the ceramic bond and the diamond particles after sintering. This phenomenon is consistent with the present invention, where the bond between the diamond particles and the vitrified bonds in the composite is good.
As shown in fig. 2, thermal properties of uncoated and coated diamonds were tested under air flow to obtain corresponding thermogravimetric analysis (TG-DTA) curves, where a is the coated diamond result and b is the uncoated diamond result. The thermogravimetric curve b1 of the uncoated diamond shows that the mass loss starts at 723 ℃. The corresponding DTA curve b2 shows a large and broad exothermic peak in the range of 685-1000 ℃. However, the curves a1 and b1 are almost straight lines. Since the ceramic coating has an effective thermal protection for diamond, there is little loss of quality of coated diamond at 1000 c, with thermal oxidation temperatures 277 c higher than uncoated diamond.
Fig. 3 shows raman spectra of uncoated diamond and two different diamonds (coated diamond and uncoated diamond) heat treated at 1000 ℃. The upper right corner of the picture is a partial enlargement. As shown in FIG. 3 (a), at 1332cm -1 Where raman peaks of diamond were observed, the spectrum confirmed that the uncoated diamond was stable before sintering. As shown in FIG. 3 (b), when the temperature was raised to 1000 ℃, the spectrum of uncoated diamond was 1332cm -1 A characteristic diamond peak appears at 1420-1660cm -1 There is a small and broad band that indicates the presence of carbon in a variety of different forms, including graphite, amorphous carbon, and diamond-like carbon. As shown in FIG. 3 (c), 1332cm of the spectrum of the coated diamond after sintering at 1000 ℃ -1 The Raman peak at this point is still evident, but is 1420-1660cm -1 The broadband at this point disappeared, indicating that the coated diamond remained stable at 1000 ℃.
To further investigate the effect of thermal oxidation, SEM images of 1000 ℃ heat treated ceramic coated diamond and uncoated diamond were analyzed. As shown in fig. 4 (a) and (b), after sintering at 1000 ℃, the uncoated diamond surface formed larger pores due to thermal damage. However, the coated diamond remained well shaped after sintering at 1000 ℃ (fig. 4 (c) and (d)). These results are consistent with TG-DTA and Raman data, further confirming the diamond protection of SBLZA glass ceramic coatings.
Example 2
A diamond abrasive is diamond coated with ceramic coating on the surface. Wherein the ceramic coating comprises the following components in percentage by mass:
Li 2 O 20％、ZnO 13％、Al 2 O 3 10％、SiO 2 46.5％、TiO 2 1.5％、B 2 O 3 9％
the preparation method comprises the following steps:
slowly adding deionized water into tetraethoxysilane, stirring at 40 ℃ for 2 hours at constant temperature, adding absolute ethyl alcohol to assist dissolution during stirring, and fully dissolving to prepare solution A;
taking analytically pure LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 Sequentially adding O zinc acetate and tetrabutyl titanate into deionized water for dissolution, and magnetically stirring at room temperature for 1h to fully mix the O zinc acetate and tetrabutyl titanate to form a mixed solution to prepare a solution B;
slowly dripping the solution B into the solution A under the condition of stirring for 1 hour at the constant temperature of 70 ℃, and dripping HNO in the process 3 The pH value of the reaction system is regulated to 3 by the solution (1 vol%) to prepare a multiple sol C solution;
the diamond is purified and then soaked in the multi-element gel C liquid to obtain the diamond with wet gel attached to the surface;
drying diamond with wet gel attached on the surface at 100 ℃ for 1.5 hours, heating to 803K (heating rate is 1 ℃/min) in a muffle furnace for 2 hours, sintering for 2 hours at 883K, and cooling to obtain the diamond.
Example 3
A diamond abrasive is diamond coated with ceramic coating on the surface. Wherein the ceramic coating comprises the following components in percentage by mass:
Li 2 O 20％、ZnO 13％、Al 2 O 3 10％、SiO 2 46.5％、TiO 2 1.5％、B 2 O 3 9％
the preparation method comprises the following steps:
slowly adding deionized water into tetraethoxysilane, stirring at a constant temperature of 30 ℃ for 2 hours, and adding absolute ethyl alcohol to assist dissolution during stirring to fully dissolve the tetraethoxysilane to prepare solution A;
taking analytically pure LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 Sequentially adding O zinc acetate and tetrabutyl titanate into deionized water for dissolution, and magnetically stirring at room temperature for 1h to fully mix the O zinc acetate and tetrabutyl titanate to form a mixed solution to prepare a solution B;
slowly dripping the solution B into the solution A under the condition of stirring for 1h at the constant temperature of 70 ℃, and dripping HNO in the process 3 The pH value of the reaction system is regulated to 4 by the solution (1 vol%) to prepare a multiple sol C solution;
and (3) purifying the diamond, soaking the diamond in the multi-component gel C solution, and stirring for 10min to obtain the diamond with the wet gel attached to the surface.
Drying diamond with wet gel attached on the surface at 120 ℃ for 0.5h, heating to 803K (heating rate is 10 ℃/min) in a muffle furnace for 2h, sintering for 2h at 883K, and cooling to obtain the diamond.
Example 4
A diamond abrasive is diamond coated with ceramic coating on the surface. Wherein the ceramic coating comprises the following components in percentage by mass:
Li 2 O 22％、ZnO 11％、Al 2 O 3 10％、SiO 2 46.5％、TiO 2 1.5％、B 2 O 3 9％
the preparation method comprises the following steps:
slowly adding deionized water into tetraethoxysilane, stirring at a constant temperature of 30 ℃ for 2 hours, and adding absolute ethyl alcohol to assist dissolution during stirring to fully dissolve the tetraethoxysilane to prepare solution A;
taking analytically pure LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 Sequentially adding O zinc acetate and tetrabutyl titanate into deionized water for dissolution, and magnetically stirring at room temperature for 1h to fully mixMixing to form a mixed solution to prepare a solution B;
slowly dripping the solution B into the solution A under the condition of stirring for 1h at the constant temperature of 70 ℃, and dripping HNO in the process 3 The pH value of the reaction system is regulated to 4 by the solution (1 vol%) to prepare a multiple sol C solution;
the diamond is purified, then soaked in the multi-element gel C liquid, and stirred for 10min to obtain the diamond with wet gel attached to the surface;
drying diamond with wet gel attached on the surface at 80 ℃ for 2 hours, heating to 803K (heating rate is 5 ℃/min) in a muffle furnace for 2 hours, sintering for 2 hours at 883K, and cooling to obtain the diamond.
Comparative example 2
A diamond abrasive differs from example 1 in that tetrabutyl titanate was not added. The inventors have found that the glass ceramic has lower nucleation and crystallization temperatures and finer and more uniform crystals than in example 1, in which tetrabutyl titanate is added, without tetrabutyl titanate.
Comparative example 3
A diamond abrasive differs from example 1 in that the pH of the multiple gel solution is 4. Experimental researches of the inventor show that too high pH of the multi-element gel solution can cause too short gel time, and each component in the gel is unevenly distributed, so that the performance of the finally prepared diamond abrasive is poor.
Comparative example 4
A diamond abrasive differs from example 1 in that the pH of the multiple gel solution is 1.
The inventor has found from experimental studies that the gel time is too long when the pH is 1. Therefore, when the pH of the multi-component gel solution is in the range of 2-3, the gel composition is uniform and time is saved.
Comparative example 5
The difference between the diamond abrasive and the example 1 is that the preparation method is as follows:
slowly adding deionized water into tetraethoxysilane, stirring at a constant temperature of 30 ℃ for 2 hours, and adding absolute ethyl alcohol to assist dissolution during stirring to fully dissolve the tetraethoxysilane to prepare solution A;
taking analytically pure LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 O, zinc acetate and tetrabutyl titanate are sequentially added into deionized water for dissolution, and are fully mixed under magnetic stirring for 1h at room temperature to form a mixed solution to prepare a solution B;
slowly dripping the solution B into the solution A under the condition of stirring for 1h at the constant temperature of 70 ℃, and dripping HNO in the process 3 The pH value of the reaction system is regulated to 2 by the solution (1 vol%) to prepare a multiple sol C solution;
the diamond is purified and then soaked in the multi-element gel C liquid to obtain the diamond with wet gel attached to the surface;
drying diamond with wet gel attached on the surface at 80 ℃ for 2 hours, heating to 803K (heating rate is 20 ℃/min) in a muffle furnace for 2 hours, sintering for 2 hours at 883K, and cooling to obtain the diamond.
Through experimental research of the inventor, the prepared diamond abrasive has incomplete surface coating, cracks and graphitization of diamond parts. It is stated that too high a heating rate can cause adverse effects in the final sample.
Comparative example 6
A diamond abrasive differs from example 1 in that zinc acetate was not added.
According to the research, compared with the example 1 without zinc acetate, the melting temperature of the base glass is reduced, and the microcrystalline ceramic with fine equiaxed grains and lower thermal expansion coefficient can be obtained; the addition of ZnO is beneficial to improving the wetting and coating performance of the microcrystalline ceramic on diamond and improving the interface bonding strength of the microcrystalline ceramic and the diamond.
Comparative example 7
A diamond abrasive differs from example 1 in that an excess of zinc acetate was added such that the mass percent of ZnO in the final ceramic coating was 20%.
The inventor researches and discovers that the crystal grains of the diamond abrasive material are coarsened.
In addition, the inventors have further studied and found that an appropriate amount of Al 2 O 3 (Al in ceramic coating) 2 O 3 The mass ratio of the modified polypropylene is 8% -14%) can be improvedThe devitrification characteristic, bending strength and chemical stability of the microcrystalline glass have important influence on the phase, microstructure and mechanical property of the microcrystalline glass precipitate during heat treatment. Proper amount of B 2 O 3 (in ceramic coating B) 2 O 3 The mass ratio of the binder is 8-14%) reduces the softening temperature of the microcrystalline ceramic, improves the mobility of the binder, and is favorable for coating the microcrystalline ceramic coating on the diamond surface.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The diamond abrasive is characterized in that the diamond abrasive is diamond coated with a ceramic coating on the surface;
the ceramic coating comprises the following components in percentage by mass: li (Li) 2 O 18％-25％、ZnO 8％-15％、Al 2 O 3 8％-14％、TiO 2 1.5％-2％、B 2 O 3 9% -10% and the balance of SiO 2 。
2. The diamond abrasive of claim 1, wherein the ceramic coating comprises, in mass percent: li (Li) 2 O 17％、ZnO 8％、Al 2 O 3 13％、SiO 2 50％、TiO 2 2% and B 2 O 3 10％。
3. A method of preparing a diamond abrasive according to claim 1 or 2, comprising the steps of:
a. purifying the surface of the diamond, and then soaking the diamond in a multi-element gel solution to obtain the diamond with gel attached to the surface;
b. c, sequentially drying, heating, oxidizing and sintering the diamond with gel attached to the surface obtained in the step a to prepare the diamond abrasive;
the solute of the polybasic gel solution comprises tetraethoxysilane and LiNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 O, zinc acetate and tetrabutyl titanate.
4. A method of preparing a multi-gel solution according to claim 3, comprising the steps of:
mixing tetraethoxysilane, absolute ethyl alcohol and water to obtain a solution A; liNO is to be carried out 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 Mixing O, zinc acetate, tetrabutyl titanate and water to obtain a solution B; and then, dropwise adding the solution B into the solution A to obtain the multi-element gel solution.
5. The preparation method according to claim 4, wherein the molar ratio of the ethyl orthosilicate, the absolute ethanol and the water in the solution A is 1 (2-4) (0.5-1.5);
in the solution B, liNO 3 、H 3 BO 3 、Al(NO 3 ) 3 ·9H 2 The total concentration of O, zinc acetate and tetrabutyl titanate is 0.6-1.0mol/L.
6. A method of preparation according to claim 3 wherein the pH of the multi-gel solution is 2-4.
7. A method according to claim 3, wherein the drying is carried out at a temperature of 80-120 ℃ for a time of 0.5-2 hours;
preferably, the temperature of the heating oxidation treatment is 783-823k, and the time is 1-2h;
preferably, the heating rate of the heating oxidation treatment is 1-10 ℃/min.
8. The method according to any one of claims 3 to 7, wherein the sintering is performed at a temperature of 863 to 903K for a time of 1 to 3 hours.
9. Use of a diamond abrasive according to claim 1 or 2 in the manufacture of an abrasive article.
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