CN108373345B - A kind of laser marking blade pretreatment method before coating - Google Patents
A kind of laser marking blade pretreatment method before coating Download PDFInfo
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- CN108373345B CN108373345B CN201810039154.XA CN201810039154A CN108373345B CN 108373345 B CN108373345 B CN 108373345B CN 201810039154 A CN201810039154 A CN 201810039154A CN 108373345 B CN108373345 B CN 108373345B
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- 238000000576 coating method Methods 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 238000010330 laser marking Methods 0.000 title claims abstract description 70
- 238000002203 pretreatment Methods 0.000 title claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 186
- 238000011282 treatment Methods 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 13
- 239000011241 protective layer Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 52
- 229910052582 BN Inorganic materials 0.000 claims description 40
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 40
- 239000003381 stabilizer Substances 0.000 claims description 33
- 239000006227 byproduct Substances 0.000 claims description 27
- 238000002791 soaking Methods 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 238000005520 cutting process Methods 0.000 claims description 21
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000001680 brushing effect Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002585 base Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 3
- 239000004519 grease Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
- 238000005530 etching Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052810 boron oxide Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 nickel nitride Chemical class 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical class O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 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
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
- C04B41/5338—Etching
- C04B41/5353—Wet etching, e.g. with etchants dissolved in organic solvents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/40—Alkaline compositions for etching other metallic material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Laser Beam Processing (AREA)
Abstract
本发明提供了一种激光打标刀片的涂层前预处理方法，将已经进行激光打标处理，具有激光打标槽的成品刀片，放入80‑95℃的热水中浸泡冲洗，去除杂质、油脂等，方便后续的酸碱溶液腐蚀处理、或者疏水层/保护层涂覆；将冲洗后的刀片置于氢氧化钠溶液中进行扩槽处理。本发明对刀具的预处理是酸或碱处理，或者涂覆处理，因为是批处理工艺，可以将大量刀具一次处理完成，之后进行硬质涂层的涂覆时便不再需要再次打标，避免了逐片打标的问题，节省了人力，更重要的是缩短了交货周期。The invention provides a pre-coating method for laser marking blades. The finished blades that have been laser marked and have laser marking grooves are soaked and rinsed in hot water of 80-95°C to remove impurities , grease, etc., to facilitate subsequent acid-base solution corrosion treatment, or hydrophobic layer/protective layer coating; place the rinsed blade in a sodium hydroxide solution for slot expansion treatment. The pretreatment of the tool in the present invention is acid or alkali treatment, or coating treatment, because it is a batch process, a large number of tools can be processed at one time, and then there is no need to mark again when the hard coating is applied. It avoids the problem of piece-by-piece marking, saves manpower, and more importantly, shortens the delivery cycle.
Description
Technical Field
The invention relates to the field of coatings, in particular to a pre-coating pretreatment method for a laser marking blade.
Background
With the gradual understanding of people on the coating, the service life, the cutting precision and the like of the cutter are greatly improved by the hard coating, so that the coating technology is widely applied to the cutter. For example, when a cubic boron nitride cutting tool is coated with a hard coating such as titanium nitride/alumina, the cutting life of the cutting tool is improved by 10% or more.
Currently, coating technology is an option for the customer, i.e. the customer can choose whether to add a coating when purchasing a tool. At present, a cutter manufacturer generally manufactures a manufactured cubic boron nitride cutter, inspects, marks and puts the manufactured cubic boron nitride cutter in storage, and then determines whether a coating needs to be added or not when receiving an order. This is mainly based on the effectiveness of the order: the synthesis, grinding forming, quality inspection and marking of the cutter often need a longer period, the coating time is relatively short, in order to supply materials to customers in the shortest time, the cutter is generally processed, the marking is put in storage, when an order is received, if the coating is not needed, the product is directly delivered, and if the coating is needed, the coating is carried out, and then the marking is carried out again.
The production process of the coating knife has the problem of repeated marking. That is, when the tool is put in storage, marking is already performed, but since the coating is thick (one micron or more) and the laser marking line is originally thin and shallow, the original marking after coating is not recognizable, and therefore, the marking needs to be performed again.
Laser marking is a single-piece processing technology, i.e. single-side or double-side marking needs to be carried out piece by piece. The material is fed, marked and blanked, wherein each laser marking needs 20 seconds, and 2000 marks need nearly twelve hours. Therefore, a large amount of labor is wasted by adding one marking process, and the laser machine is worn, and most seriously, the delivery period is prolonged.
Disclosure of Invention
The invention provides a pre-coating pretreatment method of a laser marking blade, which solves the problem that the blade coating needs to be subjected to laser marking again in the prior art.
The technical scheme for realizing the invention is as follows: before coating, the blade is pretreated, and the pretreatment ensures that secondary marking treatment is not needed after coating without adjusting a coating process. That is, after coating, the marking is still legible. The marking line is marked in a thickening way, so that the marking line can be still identified after the coating.
The pretreated blade is a blade which is subjected to synthetic processing, laser marking and qualified quality inspection, and the blade is a hard alloy blade, a ceramic blade, a diamond blade, a cubic boron nitride blade and the like. Polycrystalline cubic boron nitride inserts are used as an example in this application.
The pretreatment of the blade means acid treatment or alkali treatment, specifically, acid etching or alkali etching. The above treatment is preferably carried out only at the scribe line of the laser marking, without causing as much as possible severe corrosion of other positions, particularly the cutting edge position of the blade.
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) putting the finished product blade which is subjected to laser marking treatment and is provided with a laser marking groove into hot water at the temperature of 80-95 ℃ for soaking and washing for 30-60min, removing impurities, grease and the like, and facilitating subsequent acid-base solution corrosion treatment or hydrophobic layer/protective layer coating;
(2) and (2) placing the blade washed in the step (1) in a sodium hydroxide solution with the concentration of 7.5-17.5mol/L for groove expanding treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water with the temperature of 90-100 ℃ and mixing, the sodium hydroxide solution contains a stabilizer, and the stabilizer is sodium carbonate or NH3·H2O-NH4Cl, the content of the stabilizer is 100 g/L.
The corrosion is mainly to enlarge the depth and the width of the marked scribing line, so that the scribing line is still cleaned and distinguished after the coating is coated. The enlargement of the scribe depth and width of the laser marking is referred to as a groove enlargement process.
The laser marked marking location is generally in the center of the plane of the tool, away from the cutting edge.
Analysis and test show that the cubic boron nitride polycrystal at the laser marking reticle position has complex physical and chemical reactions, and besides the gasified (sublimed) volatilized cubic boron nitride, a large amount of cubic boron nitride has phase change and is restored to the hexagonal phase from the cubic phase.
It is understood that the boron nitride phase change at the marking site is: according to the laser marking principle, high-energy laser is converged at a marking position, and cubic boron nitride at the marking position is instantly gasified and removed by the heat of the laser, so that a scribed line is formed. In fact, laser marking has an effect on the material of the body part in addition to gasifying part of the material of the surface, the heat generated by the laser forms a thermal melting or thermal damage layer with a certain depth around the scribed line, and the cubic boron nitride is changed into the hexagonal boron nitride under the action of the heat of the laser.
Since the marking position is far from the cutting edge (actual use position), even if the marking position is seriously hot-melted or thermally damaged, the marking has little influence on the cutting use of the cutter. It is for this reason that laser marking has found widespread use in the production of cubic boron nitride with little attention paid to phase changes in the boron nitride material at the scribe line sites. The technical scheme is provided based on the fact that the phase change of boron nitride at the scribing position is found and the difference between a boron nitride phase change body and a body is analyzed.
As analyzed above, at the marking location, the cubic boron nitride around the scribe line returns to the active hexagonal phase, which provides an advantage for selective etching. Hexagonal phase boron nitride is much easier to etch than cubic phase. Therefore, the blade after scribing can be put into the selective corrosive liquid, the hexagonal boron nitride at the scribing position can be completely or partially removed by the corrosive liquid, the scratch is enlarged, and the cutter body, particularly the cutting edge part of the cutter body, is not damaged by the corrosive liquid.
And (3) corroding the hexagonal boron nitride by using a sodium hydroxide corrosive liquid, specifically, soaking and washing by using hot water to remove loose hexagonal boron nitride in the laser marked scribing line, and then further corroding by using a sodium hydroxide aqueous solution to remove part or all of the hexagonal boron nitride left in the scribing line.
In the etching process, as the hexagonal phase boron nitride to be removed only exists in the laser marked scribing line, the quality of the material to be removed by etching is extremely small, so that the adopted alkali concentration is small, and the raw material cost and the environmental protection cost are low. And the damage of the etching solution to the parts of the cutter body except the scribing can be further reduced by adopting low alkali concentration. Specifically, the proportion of hot water in the aqueous solution of sodium hydroxide is 30-70% (mass-volume ratio, Kg/L), and the concentration of sodium hydroxide in the solution is far lower than that of sodium hydroxide for removing hexagonal boron nitride and purifying cubic boron nitride in production.
The corrosion is limited to micro-scale due to long-term corrosionWithin small scribe lines to avoid OH in alkali solution in the scribe lines-The concentration of ions fluctuates, and the corrosive liquid needs to be stirred continuously in the corrosive liquid. In addition, in order to maintain OH in the sodium hydroxide solution in a minute scribe region-The ion concentration is stable, and optionally, an alkali stabilizer, such as sodium carbonate, NH, is provided in the corrosive liquid3·H2O-NH4Cl, and the like.
The consumables and the equipment required in the process of corroding the hexagonal boron nitride at the scribing position are all possessed in the production of the cubic boron nitride, and extra purchase is not needed.
By controlling the components, proportion, temperature and treatment time of the corrosive liquid, the width and depth of the laser marked scribing line are increased by more than 1 time after treatment, but not more than 4 times. The increase in width and depth is too small, the scribe remains difficult to identify after coating; and too much increase may cause deformation of the marking indicia.
In addition to the formation of hexagonal boron nitride, there are other by-products such as boron oxide (high temperature oxidation product of cubic boron nitride), titanium nitride and/or oxide (high temperature nitridation/oxidation product of binder titanium in polycrystalline cubic boron nitride, or unvaporized titanium nitride binder), aluminum nitride and/or oxide (high temperature nitridation/oxidation product of binder aluminum in polycrystalline cubic boron nitride), nickel nitride and/or oxide (high temperature oxidation product of binder nickel in polycrystalline cubic boron nitride), cobalt nitride and/or oxide (high temperature oxidation product of binder cobalt in polycrystalline cubic boron nitride), chromium nitride and/or oxide (high temperature oxidation product of binder chromium in polycrystalline cubic boron nitride), and the like. Among them, titanium nitride, chromium nitride, and aluminum oxide have a large influence on the subsequent coating.
In fact, laser marking scribes become unclear after coating, mainly because the depth and the width of the scribes are narrowed due to the fact that the coating fills the scribes, and therefore the application mainly adopts pretreatment of increasing the width and the depth of the scribes to avoid unclear scribing after coating. While a careful analysis of the process of filling the coating reveals that the thickness of the coating is typically several microns, while the depth and width of the scribe lines are discernible to the human eye, typically between tens and hundreds of microns, it is generally understood that a coating several microns thick filled into tens to hundreds of microns of scribe lines should not have such a large effect on the scribe lines that a large portion of the scribe lines are filled. The score lines are filled with coating material well beyond the thickness of the coating, in large part because of preferential film growth of the coating at the score line locations. The probable reason is that titanium nitride, chromium nitride and aluminum oxide which are byproducts of laser scribing form a large number of nucleation centers, and the growth of the coating at the scribing position is promoted. Therefore, in addition to the pretreatment of the width and depth of the scribe line, which is proposed in the foregoing, the removal of specific byproducts in the scribe line, such as titanium nitride, chromium nitride, aluminum oxide (the residues of these byproducts can promote nucleation growth of hard coatings such as titanium nitride, titanium aluminum nitride, chromium nitride, aluminum oxide, etc. at the scribe line), etc., can further effectively avoid the problem of unclear laser marking after coating.
And (3) titanium nitride byproducts exist at the laser marking position, soaking the blade subjected to the groove expanding treatment in the step (2) in a mixed solution of hydrogen peroxide and sodium hydroxide for 20-50min, or soaking the blade subjected to the groove expanding treatment in the step (2) in a mixed solution of nitric acid and hydrofluoric acid in a volume ratio of 1:1 for 1-10min, and removing the titanium nitride byproducts.
And (3) chromium nitride byproducts exist at the laser marking position, and the blade subjected to groove expanding treatment in the step (2) is placed in a mixed solution of sodium hydroxide and trisodium citrate dihydrate in a mass ratio of 10:1 to be treated to remove the chromium nitride byproducts.
And (3) an alumina byproduct exists at the laser marking position, and the blade subjected to the groove expanding treatment in the step (2) is placed in a hydrochloric acid solution with the mass concentration of 30% for treatment for 2-6min to remove the alumina byproduct.
Before removing the titanium nitride, chromium nitride or aluminum oxide by-products, soaking the blade subjected to the groove expanding treatment in the step (2) in pure water for 15-20 min.
Before removing the specific by-products in the laser marking scribing, it is ensured that the boron oxide in the scribing is dissolved and removed, especially when the specific by-products are removed by using an alkaline solution, because the acid-base concentration in the microenvironment of the scribing area is seriously affected by the aqueous solution (boric acid) of the boron oxide. For the purpose of boron oxide removal, the blade may be subjected to an additional soaking water wash before the above-mentioned removal of the specific by-products, even though the water wash treatment may have been carried out for a short time after the previous slot-expanding step. The water wash time for boron oxide removal should not be less than 5 minutes.
And (3) placing the blade subjected to the groove expanding treatment in the step (2) in a sodium hydroxide solution with the concentration of 25-30mol/L to polish the laser marking groove for 10-20 s. In order to prevent the subsequent coating from preferentially growing in the laser marking scribe, further, there is a scribe polishing process in addition to deepening and widening of the laser marking scribe and removing specific by-products such as titanium nitride, chromium nitride, aluminum oxide, and the like.
According to a general understanding of film growth, a rough surface facilitates the attachment of film-forming groups but does not facilitate their desorption, i.e., a rough surface facilitates nucleation growth of the film, and thus, polishing the scribe lines facilitates preventing preferential growth of subsequent coatings thereat. The polishing process in scribing the laser marking position of the present application is preferably a solution method for compatibility with the previous solution etching process of enlarging the groove, removing a specific by-product, and the like. Solution polishing is a common process, but in the production of superhard materials, grinding and other methods are generally adopted for polishing, mainly because the superhard materials, especially the superhard materials such as polycrystalline cubic boron nitride and the like, have various substances such as cubic boron nitride and a binder, and the solution polishing is difficult to control without corroding the binder. The research of the application finds that the concentration of the hexagonal boron nitride corrosion solution is properly increased, the hexagonal boron nitride polycrystal (containing the hexagonal boron nitride particles and the binder after oxidation/nitridation) is quickly corroded in a short time, the surface roughness in the marking line of the laser marking can be greatly reduced, meanwhile, the cutter body is not obviously damaged, although the roughness is still relatively larger than the surface (subjected to fine grinding processing) of the cutter body outside the marking area, the preferential film forming of the coating at the marking position is greatly reduced. The etching solution for polishing treatment is: the components are the same as the tank expanding solution, but the concentration is increased, the content of sodium hydroxide is 25-30mol/L, and because the corrosion time is short, a stabilizing agent is not needed. The polishing time is strictly controlled within 20 seconds, and the influence of high-concentration corrosive liquid on the cutter body is prevented.
In the three pretreatment processes, in order to further ensure that even slight corrosion does not occur at the cutting edge of the cutter, optionally, before the corrosion treatment, the cutting edge is subjected to hydrophobic treatment or coated with a protective layer to prevent corrosive liquid from reaching. After the soaking and washing in the step (1) are carried out, carrying out hydrophobic treatment or coating of a protective layer on the cutting edge of the blade by adopting a roller batch brushing process. The hydrophobic treatment or the coating of the protective layer adopts a brushing process, namely, the arranged cutters are brushed with the hydrophobic agent or the protective layer in batch by adopting rollers and the like, and the rollers only contact with the cutting edge of the cutter body and the side surface of the cutter body but not contact with the upper surface and the lower surface of the cutter body, especially not contact with the marking area in the center of the upper surface and the lower surface of the cutter body.
After the pretreatment is completed, the coating process can be performed. Generally, the coating process includes tool blasting, solvent cleaning, water washing, coating, inspection, and the like. The above-described pre-treatment of the tool and the solvent cleaning steps of the coating process can be combined, i.e. grit blasting followed by solvent cleaning, followed by acid or base pre-treatment (to extend scribing/removal of characteristic by-products/polishing for laser marking), followed by water washing (to clean the solvent and acid base), coating, inspection. This saves one water washing step.
The invention has the beneficial effects that: the pretreatment of the cutter is acid or alkali treatment or coating treatment, because of batch treatment process, a large number of cutters can be treated at one time, and then the coating of the hard coating is carried out without marking again, thereby avoiding the problem of marking piece by piece, saving manpower and more importantly shortening the delivery cycle.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) scribing a groove on a blade, carrying out laser marking treatment at the position of the groove, then carrying out laser marking treatment, and soaking and washing the blade with the groove scribed by the laser in hot water at 80 ℃ for 30 min;
(2) and (3) placing the blade washed in the step (1) in a sodium hydroxide solution with the concentration of 7.5mol/L for groove expanding treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 90 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
Example 2
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) scribing a groove on the blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at 90 ℃ for 45 min;
(2) and (3) placing the blade washed in the step (1) in a sodium hydroxide solution with the concentration of 10mol/L for groove expanding treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water with the temperature of 95 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer which is NH3·H2O-NH4Cl, the content of the stabilizer is 100 g/L.
Example 3
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) scribing a groove on the blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at 95 ℃ for 60 min;
(2) and (3) placing the blade washed in the step (1) in a sodium hydroxide solution with the concentration of 17.5mol/L for groove expanding treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
Example 4
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) scribing a groove on the blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at 80 ℃ for 60 min;
(2) adopting a brushing process, brushing the arranged cutters with a hydrophobic agent or a protective layer in batch by using a roller, and carrying out hydrophobic treatment or coating the protective layer on the cutting edge of the cutter;
(3) and (3) placing the blade treated in the step (2) in a sodium hydroxide solution with the concentration of 17.5mol/L for slot expansion treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
Example 5
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) scribing a groove on the blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at 90 ℃ for 50 min;
(2) and (3) placing the blade treated in the step (1) in a sodium hydroxide solution with the concentration of 17.5mol/L for slot expansion treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
Removing titanium nitride: soaking the blade treated in the step (2) in a mixed solution of hydrogen peroxide and sodium hydroxide for 35 min; or placing the blade treated in the step (2) in a mixed solution of nitric acid and hydrofluoric acid with the volume ratio of 1:1 for soaking for 5 min.
Example 6
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) scribing a groove on the blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at 95 ℃ for 30 min;
(2) and (3) placing the blade treated in the step (1) in a sodium hydroxide solution with the concentration of 17.5mol/L for slot expansion treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
Removing titanium nitride: soaking the blade treated in the step (2) in a mixed solution of hydrogen peroxide and sodium hydroxide for 50 min; or placing the blade treated in the step (2) in a mixed solution of nitric acid and hydrofluoric acid with the volume ratio of 1:1 for soaking for 10 min.
Example 7
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) cutting a groove on a blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at the temperature of 80-95 ℃ for 30-60 min;
(2) adopting a brushing process, brushing the arranged cutters with a hydrophobic agent or a protective layer in batch by using a roller, and carrying out hydrophobic treatment or coating the protective layer on the cutting edge of the cutter;
(3) and (3) placing the blade washed in the step (2) in a sodium hydroxide solution with the concentration of 17.5mol/L for groove expanding treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
Removing chromium nitride: and (4) placing the blade treated in the step (3) into a mixed solution of sodium hydroxide and trisodium citrate dihydrate in a mass ratio of 10:1 for treatment.
Example 8
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) cutting a groove on a blade, carrying out laser marking treatment on the groove, and then soaking and washing the blade in hot water at the temperature of 80-95 ℃ for 30-60 min;
(2) adopting a brushing process, brushing the arranged cutters with a hydrophobic agent or a protective layer in batch by using a roller, and carrying out hydrophobic treatment or coating the protective layer on the cutting edge of the cutter;
(3) and (3) placing the blade washed in the step (2) in a sodium hydroxide solution with the concentration of 17.5mol/L for groove expanding treatment.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
And (3) an alumina byproduct exists at the laser marking position, and the blade subjected to the groove expanding treatment in the step (2) is placed in a hydrochloric acid solution with the mass concentration of 30% for treatment for 2-6min to remove the alumina byproduct.
Example 9
In order to prevent the subsequent coating from preferentially growing in the laser marking scribing, a polishing treatment step can be added after the treatment of the examples 1 to 8, namely, the blade after the groove expanding treatment or the removal of the by-products is put into a sodium hydroxide solution with the concentration of 25 to 30mol/L for polishing treatment for 10 to 20 seconds.
Example 10
A pre-coating pretreatment method for a laser marking blade comprises the following steps:
(1) placing the blade subjected to laser marking treatment and provided with the groove carved by laser into hot water at 95 ℃ for soaking and washing for 30 min;
(2) the blades are arranged in order, the cutting edges are exposed, and the cutting edges of the blades are coated with a water repellent agent or a protective film from the side. The laser marking surfaces are taken as the upper surface and the lower surface, the rest surfaces are taken as the side surfaces, the laser marking is carried out on the upper surface and the lower surface, and the laser marking surfaces are coated from the side surfaces and cannot cover the marking positions;
(3) and (3) placing the blade washed in the step (2) in a sodium hydroxide solution with the concentration of 17.5mol/L for groove expanding treatment.
(4) Removing titanium nitride, and soaking in a mixed solution of nitric acid and hydrofluoric acid at a volume ratio of 1:1 for 5 min.
The sodium hydroxide solution is prepared by adding sodium hydroxide into water of 100 ℃ and mixing, wherein the sodium hydroxide solution contains a stabilizer, the stabilizer is sodium carbonate, and the content of the stabilizer is 100 g/L.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A pre-coating pretreatment method for a laser marking blade is characterized by comprising the following steps:
(1) putting the polycrystalline cubic boron nitride blade subjected to laser marking treatment into hot water at the temperature of 80-95 ℃ for soaking and washing for 30-60 min;
(2) and (2) placing the blade washed in the step (1) in a sodium hydroxide solution with the concentration of 7.5-17.5mol/L for groove expanding treatment.
2. The pre-coating pretreatment method for a laser marking blade according to claim 1, characterized in that: the sodium hydroxide solution is prepared by adding sodium hydroxide into water with the temperature of 90-100 ℃ and mixing.
3. The pre-coating pretreatment method for laser marking blades according to claim 2, characterized in that: the sodium hydroxide solution contains a stabilizer which is sodium carbonate or NH3·H2O-NH4Cl, the content of the stabilizer is 100 g/L.
4. The pre-coating pretreatment method for a laser marking blade according to claim 1, characterized in that: and (3) titanium nitride byproducts exist at the laser marking position, soaking the blade subjected to the groove expanding treatment in the step (2) in a mixed solution of hydrogen peroxide and sodium hydroxide for 20-50min, or soaking the blade subjected to the groove expanding treatment in the step (2) in a mixed solution of nitric acid and hydrofluoric acid in a volume ratio of 1:1 for 1-10min, and removing the titanium nitride byproducts.
5. The pre-coating pretreatment method for a laser marking blade according to claim 1, characterized in that: and (3) chromium nitride byproducts exist at the laser marking position, and the blade subjected to groove expanding treatment in the step (2) is placed in a mixed solution of sodium hydroxide and trisodium citrate dihydrate in a mass ratio of 10:1 to be treated to remove the chromium nitride byproducts.
6. The pre-coating pretreatment method for a laser marking blade according to claim 1, characterized in that: and (3) an alumina byproduct exists at the laser marking position, and the blade subjected to the groove expanding treatment in the step (2) is placed in a hydrochloric acid solution with the mass concentration of 30% for treatment for 2-6min to remove the alumina byproduct.
7. The pre-coating pretreatment method for laser marking blades according to any of claims 4 to 6, characterized in that: before removing the titanium nitride, chromium nitride or aluminum oxide by-products, soaking the blade subjected to the groove expanding treatment in the step (2) in pure water for 15-20 min.
8. The pre-coating pretreatment method for a laser marking blade according to claim 1, characterized in that: and (3) placing the blade subjected to the groove expanding treatment in the step (2) in a sodium hydroxide solution with the concentration of 25-30mol/L to polish the laser marking groove for 10-20 s.
9. The pre-coating pretreatment method for a laser marking blade according to claim 1, characterized in that: after the soaking and washing in the step (1) are carried out, carrying out hydrophobic treatment or coating of a protective layer on the cutting edge of the blade by adopting a roller batch brushing process.
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| JP3878755B2 (en) * | 1998-10-30 | 2007-02-07 | 京セラ株式会社 | Ceramic substrate |
| WO2000078554A1 (en) * | 1999-06-22 | 2000-12-28 | Omg Ag & Co. Kg | Laser marking compositions and method |
| CN101533771A (en) * | 2009-03-03 | 2009-09-16 | 浙江水晶光电科技股份有限公司 | A laser marking method on wafer surface |
| CN102049538B (en) * | 2009-10-28 | 2012-08-08 | 河南富耐克超硬材料股份有限公司 | Cubic boron nitride blade and preparation method thereof |
| GB2481382A (en) * | 2010-06-21 | 2011-12-28 | Hardie James Technology Ltd | Method for forming a marked coated cementitious substrate |
| KR20140084370A (en) * | 2012-12-24 | 2014-07-07 | 주식회사 에스코넥 | Method for forming pattern on surface of metal materials using a masking and chamical etching |
| CN103272527A (en) * | 2013-05-28 | 2013-09-04 | 柳州市大荣非金属材料有限公司 | High temperature and high pressure direct synthesis method of cubic boron nitride in titanium nitride plated coating |
| GB2543514B (en) * | 2015-10-20 | 2020-04-01 | Ecorenew Dmcc | A Method for Preserving a Mark on a Metallic Workpiece |
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