CN102732866A - Thermal-sprayed ceramic coating surface hole sealing method - Google Patents
Thermal-sprayed ceramic coating surface hole sealing method Download PDFInfo
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- CN102732866A CN102732866A CN2012101896845A CN201210189684A CN102732866A CN 102732866 A CN102732866 A CN 102732866A CN 2012101896845 A CN2012101896845 A CN 2012101896845A CN 201210189684 A CN201210189684 A CN 201210189684A CN 102732866 A CN102732866 A CN 102732866A
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Abstract
The invention provides a thermal-sprayed ceramic coating surface hole sealing method. The method comprises the steps that: (1) a part containing a thermal-sprayed ceramic coating is sensitized in an acid solution containing Sn<2+>; (2) the part is activated in an acidic solution containing Pd<2+>; and (3) chemical nickel plating is carried out in a chemical plating liquid containing a reducing agent and nickel salt. With the method provided by the invention, defects such as micro cracks and shrinkage holes on the surface of the thermal-sprayed ceramic coating are substantially reduced, and a thermal-sprayed ceramic coating surface with low surface roughness, wear resistance, corrosion resistance, and good high-temperature resistance can be obtained. The method provided by the invention is advantaged in simple process, low cost, low requirements on equipment, and no pollution.
Description
Technical field
The invention belongs to the chemical conversion treatment field, be specially the method for the nickeliferous mixture plating of a kind of usefulness.
Background technology
Thermal Sperayed Ceramic Coatings is applied to industries such as Aeronautics and Astronautics, chemical machinery, high speed printing packing in a large number with its good performance such as wear-resisting, corrosion-resistant, high temperature resistant.But defectives such as a large amount of tiny cracks that the ceramic coating that thermospray obtains surface exists, shrinkage cavity have had a strong impact on its surface quality.At present; Thermal Sperayed Ceramic Coatings surface-sealing method is a lot; Sealing of hole treatment process commonly used has the organic system hole sealing agent, inorganicly is hole sealing agent and adds heat diffusion treatment etc., works in the environment of high temperature, deep-etching but sealing of hole treatment process commonly used is difficult to adapt to ceramic coating.
Therefore, be necessary to propose effective sealing of hole treatment process, to improve wear-resisting, corrosion-resistant, the resistance to elevated temperatures of ceramic coating.
Summary of the invention
Weak point to prior art exists the objective of the invention is to propose a kind of thermal Sperayed Ceramic Coatings surface-sealing method.
The technical scheme that realizes the object of the invention is:
A kind of thermal Sperayed Ceramic Coatings surface-sealing method comprises step:
1) will there be the parts of thermal Sperayed Ceramic Coatings to place and contain Sn
2+Acidic solution in sensitization;
2) containing Pd
2+Acidic solution in activation;
3) chemical nickel plating in the chemical plating fluid that contains reductive agent and nickel salt.
Wherein, said step 1) also comprises the step that places spirituous solution to clean the parts that thermal Sperayed Ceramic Coatings is arranged, and the parts after will cleaning then place and contain Sn
2+With sensitization in the hydrochloric acid soln of 12～20g/L, clean after the sensitization and dry.Ceramic coating surface after the sensitization can obtain hydrolysis resultant Sn (OH) Cl and Sn (OH) through flushing
2, polymerization generates the spawn Sn that is slightly soluble in water then
2(OH)
3Cl.These hydrolysates and polymer deposition thereof form a layer thickness and reach the material that be similar to gel of several nanometers to the hundreds of nanometer thickness on the ceramic coating surface.These jellies are attached to the ceramic coating surface, can adsorb a large amount of nickel ions, play the effect of producer.
Wherein, contain Sn in the said step 1)
2+Acidic solution in contain the SnCl of 16～18g/L
2With the hydrochloric acid of 12～15g/L, the time of sensitization is 25～35min.
Wherein, said step 2) containing the PdCl of 0.4～0.8g/L
2With activation in the hydrochloric acid soln of 12～15g/L, the activatory time is 25～35min, cleans after the activation and dry.Pd in the activation solution
2+Diffuse into spawn Sn
2(OH)
3Among the Cl, and with wherein Sn
2+React, generate the Pd atom and be deposited on the ceramic coating surface with particulate state.Be equivalent in the ceramic coating surface attachment the very thin catalyst film of one deck, this layer film plays the effect that causes the chemical nickel plating reaction when nickel plating begins.
Wherein, said step 3) is to contain tensio-active agent, complexing agent, reductive agent and NiSO
4Chemical plating fluid in electroless plating, clean after the electroless plating and dry; The surfacing and the polishing of the parts after then electroless plating being handled.
Wherein, the reductive agent in the said step 3) is NaH
2PO
2, concentration is controlled at 20～40g/L in the nickel process.
Wherein, Said tensio-active agent is a kind of in sodium laurylsulfonate, sodium lauryl sulphate, the dioctyl sodium sulfosuccinate; The content of tensio-active agent is 1.3～1.7g/L; Said complexing agent is a kind of in Trisodium Citrate or EDTA disodium salt, the trolamine, and complexing agent content is 50～80g/L.Tensio-active agent can move by speeding-up ion in the electroless plating process, thereby improve electroless plating speed as a kind of AS; The effect of complexing agent is to prevent to generate the plating defect that alkali formula nickel salt deposition is caused, and in order to obtain fine and close more coating, must add an amount of complexing agent.
Wherein, the temperature of said chemical nickel plating is 40～60 ℃, and the pH value of using ammoniacal liquor to keep chemical plating fluid in the nickel process is 8～9, and the chemical nickel plating time is 1～5h.
Wherein, keep reductive agent and NiSO in the chemical plating fluid with the method for adding chemical plating fluid in the said nickel process
4Concentration is 20～40g/L and 20～40g/L.
The parts that thermal Sperayed Ceramic Coatings is arranged of the surface-sealing that method of the present invention prepares.
The parts of the thermal Sperayed Ceramic Coatings of the surface-sealing that the method that the present invention proposes prepares are high temperature resistant in preparation, the application in the device of erosion and wear resistant.
Beneficial effect of the present invention is:
Method of the present invention can obviously reduce defectives such as the surperficial tiny crack of thermal Sperayed Ceramic Coatings, shrinkage cavity, and it is low that method of the present invention can obtain surfaceness, the thermal Sperayed Ceramic Coatings surface wear-resisting, corrosion-resistant, that resistance to elevated temperatures is good.This method technical process is simple, and cost is lower, and equipment requirements is low, and is pollution-free.
Description of drawings
Fig. 1 is operation technological process figure of the present invention;
Fig. 2 and 3 is thermospray Al of embodiment 1
2O
3Ceramic coating surface-sealing cross-reference figure, wherein Fig. 2 is thermospray Al
2O
3Photo before the ceramic coating surface-sealing, wherein a figure magnification is 100 times, 50 times of b figure magnifications;
Fig. 3 is thermospray Al
2O
3Photo behind the ceramic coating surface-sealing, wherein a figure magnification is 100 times, 50 times of b figure magnifications.
Embodiment
With following most preferred embodiment the present invention is described, but is not used for limiting scope of the present invention at present.
Employed roughness measuring instrument is the TR220 roughmeter in the instance of the present invention, useful range: Ra:0.025-12.5 μ m, and highest resolution: 0.001 μ m, measuring error :≤± 10%, the needle point angle: 90 °, calibration block roughness: Ra 0.053.This measures sample length: 0.8mm in two kinds of samples, and each surveys 5 points, and each point is surveyed 3 times, averages.
Embodiment 1:
Step 1: in printing packaging applicator roll surface spraying graded ceramics coating, the surface ceramic layer is Al with the air plasma spray mode
2O
3
Step 2:, clean and finish to be placed on 100 ℃ of oven dry in the baking oven with the printing packaging applicator roll surface after the alcohol wash spraying;
Step 3: the applicator roll surface ceramic layer after the alcohol wash is immersed in the sensitizing solution for preparing in advance, and continuous rotary rollers (60r/min), make the fully sensitization of applicator roll surface ceramic layer.Sensitizing solution consist of SnCl
22H
2O:20g/L, HCl (concentration is 20%): 70ml/L, sensitization time 30min.It is 7 that sensitization finishes back use deionized water rinsing applicator roll surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 4: the applicator roll ceramic layer after the sensitization processing is immersed in the activation solution for preparing in advance, and continuous rotary rollers (60r/min), make the fully activation of applicator roll surface ceramic layer.Activation solution consists of PdCl
2: 0.5g/L, HCl (concentration is 20%): 70ml/L, soak time 30min.It is 7 that activation finishes back use deionized water rinsing applicator roll surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 5: the applicator roll ceramic layer after the activation treatment is immersed in the chemical plating fluid for preparing in advance, and continuous rotary rollers (5r/min), chemical plating fluid consists of main salt NiSO
46H
2O:68g/L; Complexing agent Trisodium Citrate: 57g/L; Reductive agent NaH
2PO
2: 40g/L; And surfactant sodium laurylsulfonate: 1.5g/L; Constantly add ammoniacal liquor in the plating process and keep the pH value at 8-9; The electroless plating temperature remains on 50 ℃.Constantly add plating bath in the electroless plating process, keep reductive agent and NiSO in the chemical plating fluid with the method for adding chemical plating fluid
4Concentration is 20～40g/L and 20～40g/L, is covered 3 hours times spent fully by nickel dam until applicator roll surface ceramic layer.It is 7 that electroless plating finishes back use tap water flushing applicator roll surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 6: with cylindrical grinder to electroless plating after the applicator roll surface carry out ground finish, grinding wheel (150 order) grinding is adopted in grinding, grinding finishes the back polished finish is carried out on the applicator roll surface.
Applicator roll surfaces A l with this method acquisition
2O
3Ceramic layer has overcome common Al
2O
3The ceramic layer surfaceness is big, can't reach the defective of design requirement, and metallic nickel is filled in Al densely
2O
3In the tiny crack of ceramic surface, the shrinkage cavity, its surfaceness is reduced largely, satisfied design requirements.The applicator roll surfaceness requires Ra=0.1, plasma spraying roller surfaces Al in the present case
2O
3Ceramic layer is surface roughness Ra=0.361 after grinding, polished finish, can't reach design requirements.Al
2O
3Ceramic layer plating nickel on surface sealing of hole is after surface roughness Ra=0.071 after the grinding, polished finish, and frictional coefficient has reduced by 4 times, can satisfy design demand well.Al behind the sealing of hole of nickel plating simultaneously
2O
3Ceramic layer can prevent effectively that corrosive fluid from infiltrating ceramic layer inside, and it is wear-resisting, corrosion resistance nature is improved.
Embodiment 2
Step 1: the surface is thermospray Al
2O
3The substrate of ceramic coating places the spirituous solution ultrasonic cleaning,
Step 2: clean and finish to be placed on 100 ℃ of oven dry in the baking oven;
Step 3: the substrate surface ceramic coating after the alcohol wash is immersed in the sensitizing solution for preparing in advance, makes surfaces A l
2O
3The abundant sensitization of ceramic coating.Sensitizing solution consist of SnCl
216g/L, HCl (concentration is 20%): 60ml/L, sensitization time 35min.It is 7 that sensitization finishes back use deionized water rinsing applicator roll surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 4: with the substrate Al after the sensitization processing
2O
3Ceramic coating is immersed in and carries out activation treatment in the activation solution for preparing in advance.Activation solution consists of PdCl
2: 0.4g/L, HCl (concentration is 20%): 60ml/L, soak time 25min.It is 7 that activation finishes back use deionized water rinse substrate surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 5: with the substrate Al after the activation treatment
2O
3Ceramic coating is immersed in and carries out electroless plating in the chemical plating fluid for preparing in advance, and chemical plating fluid consists of NiSO
440g/L; Complexing agent EDTA disodium salt: 50g/L; Reductive agent NaH
2PO
2: 40g/L; And surfactant sodium lauryl sulphate: 1.3g/L; Constantly add ammoniacal liquor in the plating process and keep the pH value about 8.5; The electroless plating temperature remains on 50 ℃.Constantly add plating bath in the electroless plating process, the concentration of keeping nickel salt and reductive agent is between 20～40g/L, until substrate surface Al
2O
3Ceramic coating is covered by nickel dam fully, 3 hours times spent.Electroless plating finishes the back with tap water rinse substrate surfaces A l
2O
3Ceramic coating to pH value is 7, places 120 ℃ of oven dry in the baking oven then;
Step 6: with cylindrical grinder to electroless plating mera surfaces A l
2O
3Ceramic coating carries out ground finish, and grinding wheel (150 order) grinding is adopted in grinding.Grinding is carried out polished finish to the surface after accomplishing.
Thermospray Al after the present embodiment sealing of hole is handled
2O
3The surface roughness Ra of ceramic coating=0.073, frictional coefficient have reduced by 4 times, can satisfy design demand well.Thermospray Al behind the sealing of hole of nickel plating simultaneously
2O
3Ceramic coating can prevent effectively that corrosive fluid from infiltrating ceramic layer inside, and it is wear-resisting, corrosion resistance nature is improved.
Embodiment 3
Step 1: the surface ceramic layer is Al
2O
3The chemical industry agitator arm place the spirituous solution ultrasonic cleaning,
Step 2: clean and finish to be placed on 100 ℃ of oven dry in the baking oven;
Step 3: be immersed in the sensitizing solution for preparing in advance the chemical industry agitator arm surface ceramic layer after the alcohol wash and constantly rotation (60r/min), make the fully sensitization of surface ceramic layer.Sensitizing solution consist of SnCl
2: 18g/L, HCl (concentration is 20%): 75ml/L, sensitization time 25min.It is 7 that sensitization finishes back use deionized water rinsing agitator arm surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 4: the agitator arm after the sensitization processing is immersed in activation solution and the constantly rotation for preparing in advance.Activation solution consists of PdCl
2: 0.8g/L, HCl (concentration is 20%): 75ml/L, soak time 35min.It is 7 that activation finishes back use deionized water rinse substrate surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 5: be immersed in the agitator arm after the activation treatment in the chemical plating fluid for preparing in advance and constantly rotation, chemical plating fluid consists of NiSO
440g/L; Complexing agent trolamine: 80g/L; Reductive agent NaH
2PO
2: 40g/L; And surfactant dioctyl sodium sulfosuccinate: 1.7g/L; Constantly add ammoniacal liquor in the plating process and keep the pH value 8.5; The electroless plating temperature remains on 50 ℃.Constantly add plating bath in the electroless plating process, the concentration of keeping nickel salt and reductive agent is covered by nickel dam until agitator arm surface ceramic layer between 20～40g/L fully, 3 hours times spent.It is 7 that electroless plating finishes back use tap water flushing agitator arm surface to pH value, places 120 ℃ of oven dry in the baking oven then;
Step 6: with cylindrical grinder to electroless plating after the agitator arm surface carry out ground finish, grinding wheel (150 order) grinding is adopted in grinding.Grinding is carried out polished finish to the surface after accomplishing.
Al after the present embodiment sealing of hole is handled
2O
3The surface roughness Ra of ceramic coating=0.072, frictional coefficient have reduced by 4 times, can satisfy design demand well.Ceramic coating behind the sealing of hole of nickel plating simultaneously can prevent effectively that corrosive fluid from infiltrating ceramic layer inside, and it is wear-resisting, corrosion resistance nature is improved.
Above embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various modification and improvement that the common engineering technical personnel in this area make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. thermal Sperayed Ceramic Coatings surface-sealing method comprises step:
1) will there be the parts of thermal Sperayed Ceramic Coatings to place and contain Sn
2+Acidic solution in sensitization;
2) containing Pd
2+Acidic solution in activation;
3) chemical nickel plating in the chemical plating fluid that contains reductive agent and nickel salt.
2. the method for claim 1 is characterized in that, said step 1) also comprises the step that places spirituous solution to clean the parts that thermal Sperayed Ceramic Coatings is arranged, and the parts after will cleaning then place and contain Sn
2+With sensitization in the hydrochloric acid soln of 12～20g/L, clean after the sensitization and dry.
3. according to claim 1 or claim 2 method is characterized in that, contains Sn in the said step 1)
2+Acidic solution in contain the SnCl of 16～18g/L
2With the hydrochloric acid of 12～15g/L, the time of sensitization is 25～35min.
4. according to claim 1 or claim 2 method is characterized in that said step 2) containing the PdCl of 0.4～0.8g/L
2With activation in the hydrochloric acid soln of 12～15g/L, the activatory time is 25～35min, cleans after the activation and dry;
5. according to claim 1 or claim 2 method is characterized in that said step 3) is to contain tensio-active agent, complexing agent, reductive agent and NiSO
4Chemical plating fluid in electroless plating, clean after the electroless plating and dry; The surfacing and the polishing of the parts after then electroless plating being handled.
6. according to claim 1 or claim 2 method is characterized in that the reductive agent in the said step 3) is NaH
2PO
2, concentration is controlled at 20～40g/L in the nickel process.
7. method as claimed in claim 5; It is characterized in that; Said tensio-active agent is a kind of in sodium laurylsulfonate, sodium lauryl sulphate, the dioctyl sodium sulfosuccinate; The content of tensio-active agent is 1.3～1.7g/L, and said complexing agent is a kind of in Trisodium Citrate or EDTA disodium salt, the trolamine, and complexing agent content is 50～80g/L.
8. according to claim 1 or claim 2 method is characterized in that the temperature of said chemical nickel plating is 40～60 ℃, and the pH value of using ammoniacal liquor to keep chemical plating fluid in the nickel process is 8～9, and the chemical nickel plating time is 1～5h.
9. according to claim 1 or claim 2 method is characterized in that, keeps reductive agent and NiSO in the chemical plating fluid with the method for adding chemical plating fluid in the said nickel process
4Concentration is 20～40g/L and 20～40g/L.
10. the parts that thermal Sperayed Ceramic Coatings is arranged of the surface-sealing for preparing of the arbitrary described method of claim 1～9.
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| CN2012101896845A CN102732866A (en) | 2012-06-08 | 2012-06-08 | Thermal-sprayed ceramic coating surface hole sealing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101896845A CN102732866A (en) | 2012-06-08 | 2012-06-08 | Thermal-sprayed ceramic coating surface hole sealing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106958015A (en) * | 2017-03-31 | 2017-07-18 | 森鹤乐器股份有限公司 | A kind of water-soluble high-efficient nickel plating antirust sealer and its compound method |
| CN107446428A (en) * | 2017-08-02 | 2017-12-08 | 江西省电力设备总厂 | A kind of hole sealing agent that Fe base amorphous coatings are prepared for HVOF |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6487005A (en) * | 1987-09-30 | 1989-03-31 | Tocalo Co Ltd | Roll for rolling process and its manufacture |
| CN101760733A (en) * | 2010-01-28 | 2010-06-30 | 西安理工大学 | Magnesium alloy chemical nickel-plating surface treatment method taking microarc oxidation process as pretreatment |
-
2012
- 2012-06-08 CN CN2012101896845A patent/CN102732866A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6487005A (en) * | 1987-09-30 | 1989-03-31 | Tocalo Co Ltd | Roll for rolling process and its manufacture |
| CN101760733A (en) * | 2010-01-28 | 2010-06-30 | 西安理工大学 | Magnesium alloy chemical nickel-plating surface treatment method taking microarc oxidation process as pretreatment |
Non-Patent Citations (3)
| Title |
|---|
| 徐昌盛，等: "金属表面陶瓷涂层封孔技术研究", 《材料保护》 * |
| 梁永政，等: "微弧氧化膜层表面化学镀Ni-P合金工艺研究", 《铸造设备与工艺》 * |
| 王爱荣: "非金属材料电镀前处理概述", 《电子电镀年会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106958015A (en) * | 2017-03-31 | 2017-07-18 | 森鹤乐器股份有限公司 | A kind of water-soluble high-efficient nickel plating antirust sealer and its compound method |
| CN107446428A (en) * | 2017-08-02 | 2017-12-08 | 江西省电力设备总厂 | A kind of hole sealing agent that Fe base amorphous coatings are prepared for HVOF |
| CN107446428B (en) * | 2017-08-02 | 2019-11-29 | 中国电建集团江西装备有限公司 | A kind of hole sealing agent preparing Fe base amorphous coating for HVOF |
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Application publication date: 20121017 |