CN110511680B - Rough polishing liquid for lead chemical mechanical polishing and oxidation resistance process - Google Patents

Rough polishing liquid for lead chemical mechanical polishing and oxidation resistance process Download PDF

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CN110511680B
CN110511680B CN201910903722.0A CN201910903722A CN110511680B CN 110511680 B CN110511680 B CN 110511680B CN 201910903722 A CN201910903722 A CN 201910903722A CN 110511680 B CN110511680 B CN 110511680B
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polishing
lead
rough
lead block
rough polishing
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CN110511680A (en
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余家欣
蔡荣
王超
孙名宏
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Southwest University of Science and Technology
Institute of Mechanical Manufacturing Technology of CAEP
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Southwest University of Science and Technology
Institute of Mechanical Manufacturing Technology of CAEP
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/005—Control means for lapping machines or devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/07—Lapping machines or devices; Accessories designed for working plane surfaces characterised by the movement of the work or lapping tool
    • B24B37/10—Lapping machines or devices; Accessories designed for working plane surfaces characterised by the movement of the work or lapping tool for single side lapping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
    • B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • 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
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The invention discloses a rough polishing solution for lead chemical mechanical polishing and an oxidation resistance process, wherein the rough polishing solution comprises the following components: grinding particles, an oxidizing agent, a metal complexing agent and deionized water; adjusting the pH of the rough polishing solution by using a pH regulator; the lead chemical mechanical polishing rough polishing solution and the corresponding polishing process can directly polish and process lead blocks after macroscopic processing; meanwhile, the rough polishing solution can effectively realize extremely high removal rate of pure lead materials, so that the surface of the rough polishing solution can simply and quickly achieve a mirror surface effect; in addition, the processed lead block surface also provides reliable early preparation work for carrying out ultra-precision processing on the lead block surface in the later period. The lead surface oxidation resistance treatment process is simple in process operation, economic and environment-friendly, and can quickly solve the problem that a surface oxidation film is generated within a few seconds after pure lead is polished, so that the detection of the surface quality is facilitated, and the use requirement in industry is also facilitated.

Description

Rough polishing liquid for lead chemical mechanical polishing and oxidation resistance process
Technical Field
The invention belongs to the technical field of precision machining, relates to chemical mechanical polishing of soft metal, and particularly relates to rough polishing solution for lead chemical mechanical polishing and an antioxidant process thereof.
Background
As a nonferrous metal with abundant resources, lead also serves as a common soft metal, has the properties of toxicity, low melting point, low rigidity, low hardness, high density, high damping, easiness in oxidation, good ductility, easiness in acid degradation resistance and the like, and is one of basic metals in modern industry. Lead has a very wide application field, and generally plays an extremely important role in various industries such as lead-acid storage batteries, weapons and ammunitions, aerospace, metallurgy, chemical engineering, electric, post and telecommunications, railways, traffic, buildings, petroleum, fishery tools, welding materials, radiation-proof materials and the like. In the manufacturing field, in order to obtain satisfactory high-precision surface quality, so that the soft metal pure lead can be applied to more extensive precision manufacturing, and meanwhile, in order to promote the development of soft metal surface processing technology, the blank of soft metal materials in the precision processing field is filled, and the research on the soft metal surface quality becomes more important at home and abroad. In general, good surface quality requires low surface roughness, low number of defects and good planarity.
The hardness of soft metals is extremely low, while lead is a typical low-hardness and easily-oxidized metal, and the selection of lead for precision machining is representative of high reliability because the hardness of lead with a purity of 99.99% is as low as HV0.23.5 MPa. Compared with other metal precision machining, the soft metal is more difficult to machine, because the extremely low hardness is easy to generate plastic flow, thermal deformation and impurity embedding in the machining process, and the characteristic of easy oxidation is also easy to cause that the real surface obtained by machining cannot be reflected after machining, therefore, the characteristics of low hardness and easy oxidation become the biggest difficult problem of machining of lead-like soft metals, and great challenge is brought to machining. In the existing mature technology, the soft metal surface processing only stops at the manual grinding stage of the waterproof abrasive paper, however, the waterproof abrasive paper grinding is far away from the requirement of the precision processing surface quality precision in the industrial field, the waterproof abrasive paper grinding usually has the defects that the global flatness cannot be achieved, SiC particles peeled off by the waterproof abrasive paper in the processing process are easily embedded into the soft metal surface, the embedded SiC particles are not easily pulled out again, and the like, and the waterproof abrasive paper grinding also stops at the micron-scale surface processing. Therefore, it is difficult to realize a soft metal surface with low surface roughness, low defect count and good flatness required in precision machining by the current-stage machining technique.
At present, due to the challenges faced by the above processing problems, there are few patents on the precise processing of soft metals such as lead in the prior art, so it is important to explore the precise surface processing of soft metals. At present, more economical precision machining focuses on polishing technology, traditional chemical polishing and mechanical polishing technologies cannot meet precision machining requirements at all, and in order to obtain a high-quality soft metal surface with near defect-free performance, the soft metal pure lead machining is carried out by combining the respective advantages of chemical polishing and mechanical polishing and adopting a method of combining chemical polishing and mechanical polishing, namely a Chemical Mechanical Polishing (CMP) technology, which is regarded as unique nano-scale global planarization technology in the field of precision machining at present. The chemical mechanical polishing technology can quickly obtain the ultra-smooth nondestructive surface through the synergistic action of the chemical reaction of the polishing solution and the mechanical grinding, and the polishing solution and the polishing process are the key points of the chemical mechanical polishing technology. Because the soft metal is adopted, micron-sized scratches are easily left on a processing surface by adopting a traditional hard polishing pad in the chemical mechanical polishing process, and the same polishing abrasive particles with high hardness or larger grain diameter are also easy to leave larger scratches on the processing surface, the surface is prevented from thermal deformation and plastic flow caused by processing in the processing process, so that the requirements for developing the chemical mechanical polishing process and the polishing solution suitable for the soft metal such as pure lead are extremely high.
Meanwhile, lead is also an easily oxidizable metal, has high chemical activity and can be used in humid air and CO2The surface oxidation is easy to occur under the contact of atmosphere or water, and the oxidized surface is covered by a layer of black and gray natural oxide film (white lead) with the molecular formula of (PbCO)3)2·Pb(OH)2. In the precision machining process, for example, the surface of pure lead after chemical mechanical polishing generates an oxide film within several seconds, and the lead white oxide film is easy to cover the real surface obtained after precision machining, which is not favorable for detecting the surface quality and is not favorable for industrial use.
Therefore, the development of the polishing solution, the polishing process and the surface oxidation resistance process which can realize the precise processing of the ultra-smooth soft metal pure lead surface is very important.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a rough polishing slurry for lead chemical mechanical polishing, comprising:
0.3-3 wt% of grinding particles, 0.03-0.1 wt% of oxidant, 0.01-0.13 wt% of metal complexing agent and the balance of deionized water; and adjusting the pH of the rough polishing solution to 4.0-6.5 by adopting a pH regulator.
Preferably, the grinding particles are colloidal silicon dioxide, and the particle size range of the grinding particles is 70-90 nm; the oxidant is hydrogen peroxide with the mass percentage concentration of 30%; the metal complexing agent is at least one of ethylenediamine tetraacetic acid or serine; the acidity regulator in the pH regulator is at least one of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid; the alkaline regulator in the pH regulator is at least one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate and potassium carbonate.
Preferably, the rough polishing slurry further includes: 0.01 to 0.03wt% of a dispersant.
Preferably, the dispersant is any one of 1-ethyl-3-methylimidazole nitrate, 1, 3-dimethylimidazole nitrate and 1-ethyl-3-methylimidazole lactic acid.
The invention also provides a lead block polishing and oxidation resisting process by adopting the rough polishing solution, which comprises the following steps:
placing a light polishing pad on a polishing disc of a polishing machine, placing a lead block to be polished on an adsorption pad of a polishing head, starting the polishing machine, polishing the lead block under the polishing pressure of 0.5-2.5 psi, the polishing environment temperature of 10-35 ℃ and the polishing rotating speed of 60-100 r/min, and dripping rough polishing liquid on the polishing pad during polishing; the distance between the polishing head and the polishing disc is 80-120 mm; the polishing head and the polishing disk rotate in the same direction and have the same or similar rotating speed;
step two, after polishing, taking down the lead block from the polishing machine, immediately washing the surface of the lead block by using absolute ethyl alcohol, and cleaning until the surface of the lead block is completely covered by the absolute ethyl alcohol and no macroscopic grinding particles, polishing and peeling lead particles and other impurities are adsorbed on the surface; the rinsing time is not less than 5 seconds,
step three, immediately carrying out high-speed spin-drying on the cleaned lead blocks, wherein spin-drying equipment adopts a centrifugal machine, the rotating speed of the centrifugal machine is set to be instantaneous 2000-6000 r/min, and the centrifugal time is not less than 3 seconds;
drying the dried lead blocks at constant temperature, wherein the drying equipment adopts an electric blower, and the drying time is not less than 30 seconds; obtaining dried lead blocks after oxidation resistance treatment;
and step five, putting the dried lead blocks subjected to the antioxidant treatment into a drying cabinet for storage.
Preferably, the light polishing pad is one of a damping cloth polishing pad or a flannelette synthetic polishing pad, and both the two polishing pads have the characteristics of fine texture, soft surface, no hair removal and the like; wherein, the flannelette of the flannelette synthetic polishing pad is artificial velvet flannelette, which contains two components of long flannelette and short flannelette; before or after each polishing, the light polishing pad needs to be manually trimmed, and the light polishing pad is brushed for not less than 1 minute by adopting a hard brush and the auxiliary deionized water; the light polishing pad needs to be maintained for a long time when being idle, namely, the finished polishing pad is soaked by deionized water, so that sundries such as residual grinding particles and the like in the polishing process are prevented from hardening and hardening on the light polishing pad, and further the use of the next light polishing pad is influenced.
Preferably, the flow rate Y mL/min of the rough polishing slurry is related to the diameter size X inches of the lead block, i.e., Y is 25X to 50X.
Preferably, the oxidizing agent in the rough polishing solution is hydrogen peroxide with a mass percentage concentration of 30%; the oxidant and the pH in the rough polishing solution have a synergistic effect, and specifically comprise the following components:
when the hydrogen peroxide accounts for 0.03wt%, the corresponding optimal pH value is 4.0-5.0; when the hydrogen peroxide is 0.05wt%, the corresponding optimal pH is 4.0-5.4; when the hydrogen peroxide is 0.07wt%, the corresponding optimal pH is 4.0-5.8; when the hydrogen peroxide accounts for 0.1wt%, the corresponding optimal pH value is 4.0-6.4; that is, the pH at which the corrosion mutation occurred on the lead surface during the polishing was 4.0 in all cases, and the pH was set so that the lead surface was exposed to corrosionThe surface has scratch mutation and pH of X2The mass percent of the hydrogen peroxide is X1，X1And X2Satisfy the relation X2＝20X1+4.4, therefore, the hydrogen peroxide mass percentage X1When the content is any one of 0.03 to 0.1wt%, the optimal pH of the rough polishing solution is 4.0 to X2。
Preferably, the rough polishing liquid is dropped onto the polishing pad in a manner of: and pumping the rough polishing solution into an injector with a stainless steel needle head, fixing the injector on a propulsion pump provided with high-voltage electrostatic equipment, enabling the stainless steel needle head to face the polishing pad, setting a certain high voltage on the stainless steel needle head of the injector by using the high-voltage electrostatic equipment, and setting the propulsion speed of the propulsion pump to drop the rough polishing solution onto the polishing pad.
Preferably, the stainless steel needle has an inner diameter of 1 to 1.5mm, a propulsion speed of a propulsion pump is Y mL/min, and a relation with a diameter size X inch of the lead block is Y ═ 25X to 50X; the high-voltage static electricity is 5-8 kV.
According to the invention, the grinding particles in the rough polishing solution can remove the lead surface reactant contacted with the grinding particles through the mechanical grinding effect of the grinding particles, and the particle size of the large grinding particles of 70-90 nm can obviously improve the removal rate of the pure lead surface material on the premise of ensuring that no large surface scratch is caused.
In the invention, the oxidant in the rough polishing solution can obviously improve the surface smoothness and brightness of the pure lead and reduce surface defects, and simultaneously, the oxidant can also oxidize the surface of the pure lead into corresponding oxides, hydroxides or metal ions so as to form a soluble complex with a metal complexing agent. The metal complexing agent can be complexed with lead ions generated during polishing, so that the concentration of free lead ions is reduced, and the generation of new lead ions is accelerated, therefore, the material removal rate of pure lead can be greatly improved, and defects caused by metal oxide or hydroxide particles and the pollution of metal ions on the surface are reduced.
The cleaning stage and the spin-drying stage both need to be operated in a state that the surface layer of the lead block is completely covered with the liquid film, and in order to prevent the surface layer of the lead block from being oxidized when contacting with air, the polished surface cannot be directly contacted with the air in the anti-oxidation treatment process, so the cleaning stage and the spin-drying stage require cleaning operation immediately after polishing is finished, and instantaneous high-speed spin-drying operation immediately after the cleaning operation is finished.
The invention at least comprises the following beneficial effects:
(1) the pH value of the rough polishing solution is in a weak acidic state; lead is an acid-prone alkali-resistant metal, scratches and even surface passivation easily occur on the polished surface under an alkaline condition, and the removal rate of the surface material gradually approaches zero along with the increase of pH and the enhancement of alkalinity; the over-corrosion phenomenon can occur on the polished surface under the strong acid condition, and the removal rate of the surface material is higher as the pH is reduced and the acidity is enhanced; therefore, the pH range detailed in the invention can ensure that the method has extremely high pure lead material removal rate and simultaneously avoids the surface over-corrosion phenomenon and passivation phenomenon in the polishing process.
(2) The lead surface oxidation resistance treatment process is simple in process operation, economic and environment-friendly, and can quickly solve the problem that an oxide film on the surface of a lead block is generated within a few seconds after the lead block is polished, so that the detection of the surface quality is facilitated, and the use requirement in industry is also facilitated; meanwhile, the invention also provides an effective scheme for long-term non-oxidation storage of lead.
(3) The lead chemical mechanical polishing rough polishing solution and the corresponding polishing process can directly polish lead blocks after macroscopic processing, such as machining of the lead blocks after machining of machine tool cutting, wire electrical discharge machining, water sand paper polishing and the like; meanwhile, the rough polishing solution can effectively realize extremely high removal rate of pure lead materials, so that the surface of the rough polishing solution can simply and quickly achieve a mirror surface effect; in addition, the processed lead block surface also provides reliable early preparation work for carrying out ultra-precision processing on the lead block surface in the later period.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a schematic structural diagram of chemical mechanical polishing of a pure lead surface according to examples 1 and 2 of the present invention;
FIG. 2 shows the original lead block after cutting by a machine tool in example 1 of the present invention;
FIG. 3 shows the original lead block after wire cut electrical discharge machining in example 2 of the present invention;
FIG. 4 is a graph showing the effect of the lead block after polishing in step one of example 1 of the present invention after being naturally oxidized (i.e., the effect of the lead block after polishing without performing an anti-oxidation treatment);
FIG. 5 is a graph showing the effect of slow oxidation of the surface of a lead block exposed to air for 2 months after polishing and anti-oxidation treatment according to example 1 of the present invention;
FIG. 6 is a graph showing the effect of the lead block after being polished and subjected to an anti-oxidation treatment in example 1 of the present invention;
FIG. 7 is a three-dimensional topography of the surface of a lead block after polishing and oxidation resistance treatment according to example 1 of the present invention;
fig. 8 is a three-dimensional topography of the surface of a lead block after polishing and oxidation resistance treatment in example 2 of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a rough polishing solution for lead chemical mechanical polishing comprises:
1wt% of colloidal silicon dioxide, 0.03wt% of hydrogen peroxide with the mass percentage concentration of 30%, 0.04 wt% of serine and the balance of deionized water; adjusting the pH of the rough polishing solution to 4.5 by adopting a pH regulator; the pH regulator adopts glacial acetic acid and ammonia water; the particle size of the colloidal silica is about 80 nm;
the lead block polishing and oxidation resistance process by adopting the rough polishing solution comprises the following steps as shown in figure 1:
placing a light polishing pad on a polishing disc of a polishing machine, placing a lead block to be polished on an adsorption pad of the polishing head, starting the polishing machine, polishing the lead block under the polishing pressure of 1.2psi, the polishing environment temperature of 24-26 ℃ and the polishing rotation speed of 60r/min, and dripping rough polishing liquid on the polishing pad during polishing; the distance between the polishing head and the polishing disk is 105 mm; the polishing head and the polishing disk rotate anticlockwise, and the rotating speed is 60 r/min; the polishing machine is a UNIPOL-1200S automatic pressure grinding polishing machine manufactured by Shenyang Kejing company; the diameter of a lead block sample is 2 inches, the thickness of the lead block sample is 3mm, the purity of the lead block sample is more than or equal to 99.99 percent, and the original processing of the lead block adopts machine tool cutting processing (as shown in figure 2); the polishing pad is a damping cloth polishing pad produced by Fuji electronic technology Limited of Wuxi city; the flow of the rough polishing solution is 50 mL/min; polishing for 30 min; as shown in fig. 1, in the chemical mechanical polishing process, a propeller pump continuously pumps a continuously stirred rough polishing slurry into a polishing pad at a certain flow rate, a sample adsorbed on a polishing head contacts with the polishing pad under the action of applied pressure, the polishing pad and the sample rotate in the same direction to continuously supplement the polishing slurry to a contact area, and the sample continuously removes surface materials under the synergistic action of chemical reaction and mechanical grinding of the polishing slurry, so that the global planarization of the surface of the sample is realized; FIG. 4 is a diagram showing the effect of the lead block polished in the first step after being naturally oxidized (i.e., the effect of the lead block polished without being subjected to an anti-oxidation treatment);
step two, after polishing, taking down the lead block from the polishing machine, immediately washing the surface of the lead block by using absolute ethyl alcohol, and cleaning until the surface of the lead block is completely covered by the absolute ethyl alcohol and no macroscopic grinding particles, polishing and peeling lead particles and other impurities are adsorbed on the surface; the rinsing time was about 10 seconds; the purpose of selecting absolute ethyl alcohol as the cleaning agent is as follows: the absolute ethyl alcohol is used as an economic and environment-friendly organic reagent, can well isolate air and prevent CO in the air2、O2Etc. are directly contacted with the surface of pure lead, thereby hindering the formation of oxide film lead white; on the other hand, the surface residues after polishing, such as abrasive grains, lead particles peeled off by polishing, and the like, are cleaned with absolute ethanol；
Thirdly, placing the cleaned lead blocks on a centrifugal machine for instantaneous high-speed centrifugal drying for 2 times, wherein the drying time is about 5 seconds each time, and the rotating speed of the centrifugal machine is set to be instantaneous 3000 r/min; the purpose of instantaneous high-speed centrifugal drying is as follows: after the surface is cleaned by adopting absolute ethyl alcohol, although the absolute ethyl alcohol is volatile, the volatilization speed is far less than the generation speed of oxide film lead white on the surface, along with the natural drying volatilization of the absolute ethyl alcohol, the edge of a solid-liquid contact (to be dried) area at the volatilization part of the absolute ethyl alcohol on the surface still forms a little lead white on the surface due to the intervention of liquid and air; the surface of the dry powder is dried by adopting a centrifugal machine to instantly dry the absolute ethyl alcohol at a high speed, so that the drying time (instant drying) of the surface of a solid-liquid contact area is greatly reduced, the time of the surface exposed to air under the condition of liquid is reduced, the probability of lead white formation is greatly reduced, and the core of the antioxidant treatment process is positioned; after the lead block is taken off from the polishing machine (the lead block is separated from a polishing pad coated with polishing liquid) and before the lead block is dried by a centrifugal machine, the surface of the lead block is in a state of being covered by a liquid film, namely, the surface of the lead block is not directly exposed to the air in the process, and once the lead block is directly contacted with the air in the whole or local area, the contact area is oxidized within a few seconds;
drying the dried lead block at constant temperature, wherein a 2000W electric blower is adopted as drying equipment, and the drying time is about 1 minute; obtaining dried lead blocks after oxidation resistance treatment;
fifthly, putting the dried lead blocks subjected to the anti-oxidation treatment into a drying cabinet for storage; FIG. 5 is a graph showing the effect of slow oxidation of the surface of a lead block after polishing and oxidation resistance treatment after exposure to air for 2 months; FIG. 6 is a diagram showing the effect of lead blocks after polishing and oxidation resistance treatment;
calculating the material removal rate by weighing the weight change of the sample before and after polishing through a balance; the polished sample surface was characterized by a white light interferometric three-dimensional profilometer (MFT3000, Rtec, USA) with a scan area of 222 μm × 177 μm during the test, and on this basis, the surface three-dimensional topography was analyzed and the surface roughness was calculated using a suitable image processing software.
And (3) testing results:
in example 1, the lead slug had a surface material removal rate of about
Figure BDA0002212625950000081
The surface roughness of the lead block is about 60nm, and the three-dimensional topography of the surface is shown in fig. 7.
Example 2:
a rough polishing solution for lead chemical mechanical polishing comprises:
1wt% of colloidal silicon dioxide, 0.1wt% of hydrogen peroxide with the mass percentage concentration of 30%, 0.12 wt% of ethylene diamine tetraacetic acid and the balance of deionized water; adjusting the pH of the rough polishing solution to 5 by adopting a pH regulator; the pH regulator adopts glacial acetic acid and ammonia water; the particle size of the colloidal silica is about 80 nm;
the lead block polishing and oxidation resistance process by adopting the rough polishing solution comprises the following steps:
placing a light polishing pad on a polishing disc of a polishing machine, placing a lead block to be polished on an adsorption pad of the polishing head, starting the polishing machine, polishing the lead block under the polishing lower pressure of 0.5psi, the polishing environmental temperature of 24-26 ℃ and the polishing rotating speed of 80r/min, and dripping rough polishing liquid on the polishing pad during polishing; the distance between the polishing head and the polishing disk is 105 mm; the polishing head and the polishing disk rotate anticlockwise, and the rotating speed is 80 r/min; the polishing machine is a UNIPOL-1200S automatic pressure grinding polishing machine manufactured by Shenyang Kejing company; the diameter of a lead block sample is 2 inches, the thickness of the lead block sample is 3mm, the purity of the lead block sample is more than or equal to 99.99 percent, and the original processing of the lead block adopts wire cut electrical discharge machining (as shown in figure 3); ChemoMet manufactured by Buehler, USATMThe polishing pad is made of artificial velvet flannelette; the flow rate of the rough polishing solution is 100 mL/min; polishing for 30 min;
step two, after polishing, taking down the lead block from the polishing machine, immediately washing the surface of the lead block by using absolute ethyl alcohol, and cleaning until the surface of the lead block is completely covered by the absolute ethyl alcohol and no macroscopic grinding particles, polishing and peeling lead particles and other impurities are adsorbed on the surface; the rinsing time was about 10 seconds;
thirdly, placing the cleaned lead blocks on a centrifugal machine for instantaneous high-speed centrifugal drying for 2 times, wherein the drying time is about 5 seconds each time, and the rotating speed of the centrifugal machine is set to be instantaneous 3000 r/min;
drying the dried lead block at constant temperature, wherein a 2000W electric blower is adopted as drying equipment, and the drying time is about 1 minute; obtaining dried lead blocks after oxidation resistance treatment;
fifthly, putting the dried lead blocks subjected to the anti-oxidation treatment into a drying cabinet for storage;
calculating the material removal rate by weighing the weight change of the sample before and after polishing through a balance; the polished sample surface was characterized by a white light interferometric three-dimensional profilometer (MFT3000, Rtec, USA) with a scan area of 222 μm × 177 μm during the test, and on this basis, the surface three-dimensional topography was analyzed and the surface roughness was calculated using a suitable image processing software.
And (3) testing results:
in example 1, the lead slug had a surface material removal rate of about
Figure BDA0002212625950000091
The surface roughness of the lead block is about 25nm, and the three-dimensional topography of the surface is shown in fig. 8.
The above embodiment 1 and embodiment 2 show that the rough polishing solution for lead chemical mechanical polishing and the polishing process corresponding thereto according to the present invention can enable pure lead polishing to have a high surface material removal rate, so that a macro-processed lead block can rapidly achieve a common mirror effect, and the surface roughness of the lead block can be smoothly reduced.
The technical scheme for surface oxidation resistance treatment after lead chemical mechanical polishing can perfectly solve the problem that oxidation occurs within seconds after lead chemical mechanical polishing, and provides powerful guarantee for industrial use and surface quality detection of high-precision pure lead. Therefore, the rough polishing solution for lead chemical mechanical polishing and the oxidation resistant process can simply, conveniently and quickly meet the requirement of the quality of a precisely processed surface.
Example 3:
a rough polishing solution for lead chemical mechanical polishing comprises:
1wt% of colloidal silicon dioxide, 0.03wt% of hydrogen peroxide with the mass percentage concentration of 30%, 0.04 wt% of serine and the balance of deionized water; adjusting the pH of the rough polishing solution to 4.5 by adopting a pH regulator; the pH regulator adopts glacial acetic acid and ammonia water; the particle size of the colloidal silica is about 80 nm;
the lead block polishing and oxidation resistance process by adopting the rough polishing solution comprises the following steps:
placing a light polishing pad on a polishing disc of a polishing machine, placing a lead block to be polished on an adsorption pad of the polishing head, starting the polishing machine, polishing the lead block under the polishing pressure of 1.2psi, the polishing environment temperature of 24-26 ℃ and the polishing rotation speed of 60r/min, and dripping rough polishing liquid on the polishing pad during polishing; the distance between the polishing head and the polishing disk is 105 mm; the polishing head and the polishing disk rotate anticlockwise, and the rotating speed is 60 r/min; the polishing machine is a UNIPOL-1200S automatic pressure grinding polishing machine manufactured by Shenyang Kejing company; the diameter of a lead block sample is 2 inches, the thickness of the lead block sample is 3mm, the purity of the lead block sample is more than or equal to 99.99 percent, and the original processing of the lead block adopts machine tool cutting processing; the polishing pad is a damping cloth polishing pad produced by Fuji electronic technology Limited of Wuxi city; polishing for 30 min; the manner of dropping the rough polishing liquid onto the polishing pad is as follows: pumping the rough polishing solution into an injector with a stainless steel needle head, fixing the injector on a propulsion pump provided with high-voltage electrostatic equipment, enabling the stainless steel needle head to face a polishing pad, setting a certain high voltage on the stainless steel needle head of the injector by using the high-voltage electrostatic equipment, setting the propulsion speed of the propulsion pump, and dripping the rough polishing solution onto the polishing pad; the inner diameter of the stainless steel needle is 1.2mm, and the propelling speed of the propelling pump is 50 mL/min; the high-voltage static electricity is 7 kV;
step two, after polishing, taking down the lead block from the polishing machine, immediately washing the surface of the lead block by using absolute ethyl alcohol, and cleaning until the surface of the lead block is completely covered by the absolute ethyl alcohol and no macroscopic grinding particles, polishing and peeling lead particles and other impurities are adsorbed on the surface; the rinsing time was about 10 seconds;
thirdly, placing the cleaned lead blocks on a centrifugal machine for instantaneous high-speed centrifugal drying for 2 times, wherein the drying time is about 5 seconds each time, and the rotating speed of the centrifugal machine is set to be instantaneous 3000 r/min;
drying the dried lead block at constant temperature, wherein a 2000W electric blower is adopted as drying equipment, and the drying time is about 1 minute; obtaining dried lead blocks after oxidation resistance treatment;
fifthly, putting the dried lead blocks subjected to the anti-oxidation treatment into a drying cabinet for storage;
calculating the material removal rate by weighing the weight change of the sample before and after polishing through a balance; the polished sample surface was characterized by a white light interferometric three-dimensional profilometer (MFT3000, Rtec, USA) with a scan area of 222 μm × 177 μm during the test, and on this basis, the surface three-dimensional topography was analyzed and the surface roughness was calculated using a suitable image processing software.
And (3) testing results:
in example 3, the lead slug had a surface material removal rate of about
Figure BDA0002212625950000101
The surface roughness of the lead block was about 45 nm.
Example 4:
a rough polishing solution for lead chemical mechanical polishing comprises:
1wt% of colloidal silicon dioxide, 0.03wt% of hydrogen peroxide with the mass percentage concentration of 30%, 0.04 wt% of serine, 0.02 wt% of 1-ethyl-3-methylimidazole nitrate and the balance of deionized water; adjusting the pH of the rough polishing solution to 4.5 by adopting a pH regulator; the pH regulator adopts glacial acetic acid and ammonia water; the particle size of the colloidal silica is about 80 nm;
the lead block polishing and oxidation resistance process by adopting the rough polishing solution comprises the following steps:
placing a light polishing pad on a polishing disc of a polishing machine, placing a lead block to be polished on an adsorption pad of the polishing head, starting the polishing machine, polishing the lead block under the polishing pressure of 1.2psi, the polishing environment temperature of 24-26 ℃ and the polishing rotation speed of 60r/min, and dripping rough polishing liquid on the polishing pad during polishing; the distance between the polishing head and the polishing disk is 105 mm; the polishing head and the polishing disk rotate anticlockwise, and the rotating speed is 60 r/min; the polishing machine is a UNIPOL-1200S automatic pressure grinding polishing machine manufactured by Shenyang Kejing company; the diameter of a lead block sample is 2 inches, the thickness of the lead block sample is 3mm, the purity of the lead block sample is more than or equal to 99.99 percent, and the original processing of the lead block adopts machine tool cutting processing; the polishing pad is a damping cloth polishing pad produced by Fuji electronic technology Limited of Wuxi city; polishing for 30 min; the manner of dropping the rough polishing liquid onto the polishing pad is as follows: pumping the rough polishing solution into an injector with a stainless steel needle head, fixing the injector on a propulsion pump provided with high-voltage electrostatic equipment, enabling the stainless steel needle head to face a polishing pad, setting a certain high voltage on the stainless steel needle head of the injector by using the high-voltage electrostatic equipment, setting the propulsion speed of the propulsion pump, and dripping the rough polishing solution onto the polishing pad; the inner diameter of the stainless steel needle is 1.2mm, and the propelling speed of the propelling pump is 50 mL/min; the high-voltage static electricity is 7 kV;
step two, after polishing, taking down the lead block from the polishing machine, immediately washing the surface of the lead block by using absolute ethyl alcohol, and cleaning until the surface of the lead block is completely covered by the absolute ethyl alcohol and no macroscopic grinding particles, polishing and peeling lead particles and other impurities are adsorbed on the surface; the rinsing time was about 10 seconds;
thirdly, placing the cleaned lead blocks on a centrifugal machine for instantaneous high-speed centrifugal drying for 2 times, wherein the drying time is about 5 seconds each time, and the rotating speed of the centrifugal machine is set to be instantaneous 3000 r/min;
drying the dried lead block at constant temperature, wherein a 2000W electric blower is adopted as drying equipment, and the drying time is about 1 minute; obtaining dried lead blocks after oxidation resistance treatment;
fifthly, putting the dried lead blocks subjected to the anti-oxidation treatment into a drying cabinet for storage;
calculating the material removal rate by weighing the weight change of the sample before and after polishing through a balance; the polished sample surface was characterized by a white light interferometric three-dimensional profilometer (MFT3000, Rtec, USA) with a scan area of 222 μm × 177 μm during the test, and on this basis, the surface three-dimensional topography was analyzed and the surface roughness was calculated using a suitable image processing software.
And (3) testing results:
in example 4, the lead slug had a surface material removal rate of about
Figure BDA0002212625950000121
The surface roughness of the lead block is about 25 nm.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (6)

1. A lead block polishing and oxidation resistance process adopting rough polishing liquid is characterized by comprising the following steps:
placing a light polishing pad on a polishing disc of a polishing machine, placing a lead block to be polished on an adsorption pad of a polishing head, starting the polishing machine, polishing the lead block under the polishing pressure of 0.5-2.5 psi, the polishing environment temperature of 10-35 ℃ and the polishing rotating speed of 60-100 r/min, and dripping rough polishing liquid on the polishing pad during polishing; the distance between the polishing head and the polishing disc is 80-120 mm; the polishing head and the polishing disk rotate in the same direction and have the same or similar rotating speed;
step two, after polishing, taking down the lead block from the polishing machine, immediately washing the surface of the lead block by using absolute ethyl alcohol, and cleaning until the surface of the lead block is completely covered by the absolute ethyl alcohol and no macroscopic grinding particles and polishing and peeling lead particle impurities are adsorbed on the surface of the lead block; the rinsing time is not less than 5 seconds,
step three, immediately carrying out high-speed spin-drying on the cleaned lead blocks, wherein spin-drying equipment adopts a centrifugal machine, the rotating speed of the centrifugal machine is set to be instantaneous 2000-6000 r/min, and the centrifugal time is not less than 3 seconds;
drying the dried lead blocks at constant temperature, wherein the drying equipment adopts an electric blower, and the drying time is not less than 30 seconds; obtaining dried lead blocks after oxidation resistance treatment;
fifthly, putting the dried lead blocks subjected to the anti-oxidation treatment into a drying cabinet for storage;
the rough polishing solution comprises:
0.3-3 wt% of grinding particles, 0.03-0.1 wt% of oxidant, 0.01-0.13 wt% of metal complexing agent and the balance of deionized water; adjusting the pH of the rough polishing solution to 4.0-6.5 by using a pH regulator; 0.01-0.03 wt% of a dispersant;
the grinding particles are colloidal silicon dioxide, and the particle size range of the grinding particles is 70-90 nm; the oxidant is hydrogen peroxide with the mass percentage concentration of 30%; the metal complexing agent is at least one of ethylenediamine tetraacetic acid or serine; the acidity regulator in the pH regulator is at least one of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid; the alkaline regulator in the pH regulator is at least one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate and potassium carbonate;
the dispersant is any one of 1-ethyl-3-methylimidazole nitrate, 1, 3-dimethyl imidazole nitrate and 1-ethyl-3-methylimidazole lactic acid.
2. The lead block polishing and oxidation resistance process using rough polishing slurry as claimed in claim 1, wherein the light weight polishing pad is one of a damping cloth polishing pad or a flannelette composite polishing pad; wherein, the flannelette of the flannelette synthetic polishing pad is artificial velvet flannelette, which contains two components of long flannelette and short flannelette; before or after each polishing, the light polishing pad needs to be manually trimmed, and the light polishing pad is brushed for not less than 1 minute by adopting a hard brush and the auxiliary deionized water; the light polishing pad needs to be maintained for a long time when being idle, namely, the finished polishing pad is soaked by deionized water.
3. The process for polishing and anti-oxidation of lead blocks by using rough polishing slurry as claimed in claim 1, wherein the flow rate of the rough polishing slurry is Y mL/min, which is related to the diameter size of the lead block X inches, i.e. Y = 25X-50X.
4. The lead block polishing and oxidation resistance process using rough polishing slurry according to claim 1, wherein the oxidizing agent in the rough polishing slurry is hydrogen peroxide with a mass percentage concentration of 30%; the oxidant and the pH in the rough polishing solution have a synergistic effect, and specifically comprise the following components:
when the hydrogen peroxide accounts for 0.03wt%, the corresponding optimal pH value is 4.0-5.0; when the hydrogen peroxide is 0.05wt%, the corresponding optimal pH is 4.0-5.4; when the hydrogen peroxide is 0.07wt%, the corresponding optimal pH is 4.0-5.8; when the hydrogen peroxide accounts for 0.1wt%, the corresponding optimal pH value is 4.0-6.4; that is, the pH at which the corrosion mutation occurred on the lead surface was 4.0 in all cases during the polishing, and the pH at which the scratch mutation occurred on the lead surface was X2The mass percent of the hydrogen peroxide is X1，X1And X2Satisfy the relation X2=20X1+4.4, therefore, the hydrogen peroxide mass percentage X1When the content is 0.03-0.1 wt%, the optimal pH of the rough polishing solution is 4.0-X2。
5. The lead block polishing and oxidation resistance process using the rough polishing slurry as set forth in claim 1, wherein the rough polishing slurry is applied to the polishing pad by a method comprising: and pumping the rough polishing solution into an injector with a stainless steel needle head, fixing the injector on a propulsion pump provided with high-voltage electrostatic equipment, enabling the stainless steel needle head to face the polishing pad, setting a certain high voltage on the stainless steel needle head of the injector by using the high-voltage electrostatic equipment, and setting the propulsion speed of the propulsion pump to drop the rough polishing solution onto the polishing pad.
6. The lead block polishing and anti-oxidation process by using the rough polishing solution as claimed in claim 5, wherein the stainless steel needle has an inner diameter of 1-1.5 mm, a propelling speed of a propelling pump is Y mL/min, and a relation with a diameter size X inch of the lead block is Y = 25X-50X; the high-voltage static electricity is 5-8 kV.
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