CN109267024A - A kind of preparation method of foam tin material - Google Patents
A kind of preparation method of foam tin material Download PDFInfo
- Publication number
- CN109267024A CN109267024A CN201811300505.4A CN201811300505A CN109267024A CN 109267024 A CN109267024 A CN 109267024A CN 201811300505 A CN201811300505 A CN 201811300505A CN 109267024 A CN109267024 A CN 109267024A
- Authority
- CN
- China
- Prior art keywords
- foam
- tin
- sputtering
- content
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Abstract
The invention discloses a kind of preparation method of foam tin material, include the following steps: to carry out vacuum magnetic-control sputtering nickel plating to polyurethane sponge；Treated conductive polyurethane sponge electrotinning in electroplate liquid will be passed through, obtain foam tin material after washing and drying.Present invention nickel plating on polyurethane sponge with vacuum magnetic-control sputtering technology, then re-plating tin, entire simple process, and polyurethane sponge needs not move through the pre-treatments such as roughening, energy conservation and environmental protection, and can be carried out extensive consecutive production, finally obtained foam tin material is detected by EDS, the content of nickel is not detected, illustrate that its content is extremely low, the content of tin has reached 99.7%, compared to the prior art, the purity of tin greatly improves, and the performance of corresponding foam tin also gets a promotion.
Description
Technical field
The invention belongs to foam metal material fields, and in particular to a kind of preparation method of foam tin material.
Background technique
The features such as foam metal is because of light, large specific surface area, high specific strength, structure are uniform, excellent energy absorption, tool
Functional and structure double attribute, is widely used in chemical industry, the energy, catalyst carrier, sound-absorbing, damping etc..Wherein steep
Foam tin is a kind of novel foam metal of the controllable high porosity in random aperture, aperture, can be widely used for catalyst carrier and subtracts
Shake sound-absorbing material.
The preparation method of conventional foam tin material, usually by polyurethane sponge by being roughened, being sensitized, activate, after dispergation
Electroless copper or chemical nickel plating are carried out, then again by electric plating method, in foam copper or one layer of the electroplating surface of nickel foam
Metallic tin, to form foam tin material.The foam tin that this method prepares, conductive layer is metallic copper or nickel, at certain
Under the conditions of a little corrosive medias, after the metallic tin of foam tin surfaces is corroded, the metallic copper or nickel of bottom can be exposed to corruption
It loses in media environment, so that the chemical characteristic of foam tin material can be changed.
To solve the above-mentioned problems, number of patent application CN201010189543.4 discloses a kind of preparation of foam tin material
Method, comprising the following steps: polyurethane sponge is successively roughened, neutralizes, presoak, activating, dispergation, it then will be after dispergation
Polyurethane sponge is in the solution that pH value is 7~10, the chemical plating stannum 10~30 minutes at a temperature of 80~95 DEG C, finally by electricity
It is tin plating, obtain foam tin material.But polyurethane sponge is immersed in strongly acidic solution by the method in roughening step, when long
Between lower polyurethane sponge be easily carbonized, subsequent production can not be carried out；In addition its process flow is complicated, chemical solvent use compared with
More, cost of material is high, and wastewater discharge is big, pollutes the environment, while also having aggravated the burden of enterprise's sewage treatment.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of preparation method of foam tin material.
The present invention provides a kind of preparation method of foam tin material, includes the following steps:
A) vacuum magnetic-control sputtering nickel plating is carried out to polyurethane sponge；
B) it will be steeped after washing and drying by step a) treated conductive polyurethane sponge electrotinning in electroplate liquid
Foam tin material.
Preferably, polyurethane sponge described in step a) with a thickness of 0.5-5mm.
Preferably, the process conditions of vacuum magnetic-control sputtering nickel plating described in step a) are as follows: background vacuum≤0.11pa, work
Make vacuum degree 0.3-0.9Pa, polyurethane sponge walking speed is 4-7m/min, argon flow 80-180sccm.
Preferably, the concrete operations of vacuum magnetic-control sputtering nickel plating described in step a) are: vacuumize, when background vacuum≤
When 0.11Pa, enters the tape transport sputtering stage after opening target power supply 2-8min, adjust target power output and argon flow, open waterway circulating
Valve is opened sputtering target power supply and is sputtered, working vacuum degree control as 0.3-0.9Pa, and target power output is controlled in 2.5-3.0KW,
Argon flow 80-120sccm is sputtered 1-3 times, then working vacuum degree is controlled as 0.3-0.4Pa, target power output control by sputtering target
System sputters 1-4 times at 3.5-4.5KW, argon flow 120-180sccm, then stops sputtering.
Preferably, the material of the sputtering target is metallic nickel.
Preferably, the component of electroplate liquid described in step b) are as follows: tin methane sulfonate, methane sulfonic acid, additive A, additive B
And water.
Preferably, the content of tin methane sulfonate is 20-50g/L in the electroplate liquid, and the content of methane sulfonic acid is 120-
180ml/L, the content of additive A are 60-100ml/L, and the content of additive B is 10-15ml/L.
Preferably, electroplating technique condition described in step b) are as follows: electroplating current 20A, electroplating current density 2.4A/
dm2, electroplating temperature is 20-25 DEG C.
Preferably, the surface density of polyurethane sponge outer layer metal tin is 400-600g/m after the plating2。
Additive A of the present invention is the S-1028 open cylinder agent A that Kun Yuan Chemical Co., Ltd. in Shanghai provides；Additive B is
The S-1028 brightener B that Shanghai Kun Yuan Chemical Co., Ltd. provides.
Currently, the research in relation to foam tin material is less, common method is chemical nickel plating or copper on foam substrate, so
Re-plating tin afterwards, but the content of other metallic elements is more in the foam tin material obtained in this way, influences foam
The performance of tin, and the foam substrate before the method chemical plating is needed by pre-treatments such as roughening, and process flow is complicated, chemistry
Solvent is using more, and cost of material is high, and wastewater discharge is big, pollutes the environment, while also having aggravated enterprise's sewage treatment
Burden.Present invention nickel plating on polyurethane sponge with vacuum magnetic-control sputtering technology, then re-plating tin, entire simple process,
And polyurethane sponge needs not move through the pre-treatments such as roughening, energy conservation and environmental protection, and can be carried out extensive consecutive production, final
The foam tin material arrived is detected by SEM/EDS, and the content of nickel is not detected, illustrates that its content is extremely low, the content of tin reaches
99.7%, compared to the prior art, the purity of tin greatly improves, and the performance of corresponding foam tin also gets a promotion.
Currently, the method for preparing foam metal material mainly has chemical plating, plating, vacuum magnetic-control sputtering plating etc..Wherein, very
Empty magnetron sputtering is since the advantages such as low energy consumption, simple process are used widely, but vacuum in existing vacuum sputtering process
Degree, target power output and argon flow will not change, and gather as number of patent application CN201110147470.7 is disclosed to polyester-type
Urethane foam base plate carries out the device and method of magnetron sputtering plating, and working vacuum degree, target power output and argon flow are kept
In a definite value.The inventor of the present application found through research that according to this method vacuum magnetic-control sputtering nickel plating, re-plating tin,
The content of nickel is more in finally obtained foam tin material, and the content of tin is accordingly reduced, and purity reduces, the performance of foam tin also phase
The decline answered.For the present invention during vacuum magnetic-control sputtering nickel plating, sputtering number is 2-7 times, and true in sputtering process
Reciprocal of duty cycle, target power output and argon flow change, working vacuum degree be 0.3-0.9Pa, target power output 2.5-3.0kW, argon
Sputter 1-3 times under throughput 80-120sccm, then working vacuum degree be 0.3-0.4Pa, target power output 3.5-4.5kW, argon
It is sputtered 1-4 times under throughput 120-180sccm, the content of nickel is extremely low in finally obtained foam tin material, and the content of tin reaches
99.7%, the purity of tin greatly improves, the performance of corresponding foam tin material also gets a promotion.
In addition, the inventor of the present application found through research that, only vacuum magnetic-control sputtering nickel plating, re-plating tin obtains
The performance of foam tin material is best, and tension and extruding rebound effect are best.According to vacuum magnetic-control sputtering copper facing, silver or chromium, then
Electrotinning, the content of other metallic elements is more in finally obtained foam tin material, and the purity of tin is lower, and performance is also corresponding
Decline.
The main ingredient of electroplate liquid used in electrotinning of the present invention is tin methane sulfonate, methane sulfonic acid, additive A, addition
Agent B and water, wherein the content of tin methane sulfonate is 20-50g/L, and the content of methane sulfonic acid is 120-180ml/L, additive A
Content is 60-100ml/L, and the content of additive B is 10-15ml/L.The inventor of the present application found through research that using this Shen
Electroplate liquid electrotinning please, and combined with above-mentioned vacuum magnetic-control sputtering nickel plating technology, the performance of obtained foam tin material is excellent
Different, long service life, foam tin material shows the elongation percentage and crushing resistance that have excellent when stress and compression.
The beneficial effects of the present invention are:
1, the nickel plating of the invention on polyurethane sponge with vacuum magnetic-control sputtering technology, then re-plating tin, entire technique are simple
It is single, and polyurethane sponge needs not move through the pre-treatments such as roughening, energy conservation and environmental protection, and can be carried out extensive consecutive production, most
The foam tin material obtained eventually is detected by SEM/EDS, and the content of nickel is not detected, illustrates that its content is extremely low, the content of tin reaches
To 99.7%, compared to the prior art, the purity of tin is greatly improved, and the performance of corresponding foam tin also gets a promotion, and is solved
Covering metal layer corrosion in tinwork by metal in prior art leads to tin plated materials function and performance failure problem.
2, for the present invention during vacuum magnetic-control sputtering nickel plating, sputtering number is 2-7 times, and true in sputtering process
Reciprocal of duty cycle, target power output and argon flow change, and the content of nickel is extremely low in finally obtained foam tin material, and the content of tin reaches
To 99.7%, the purity of tin is greatly improved, and the performance of corresponding foam tin material also gets a promotion.
3, there is polyurethane sponge carbonization when the present invention solves the polyurethane sponge conductive treatment in foam process of tin
Problem guarantees to carry out electrotinning subsequent technique under the premise of three-dimensional porous structure is not destroyed.
4, preparation method of the invention is simple, the production time is short, low energy consumption, energy conservation and environmental protection, and can be carried out extensive continuous
Property production, and it is good by the binding force of the vacuum magnetic-control sputtering technology tin deposited and polyurethane foam, substantially increase production
Efficiency.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that foam tin material amplifies 200 times.
Fig. 2 is the scanning electron microscope (SEM) photograph that foam tin material amplifies 2000 times.
Fig. 3 is foam tin material EDS test result figure.
Fig. 4 is the scanning electron microscope (SEM) photograph that foam tin material amplifies 300 times.
Fig. 5 is the foam tin crystalline substance wall thickness figure that foam tin material is measured by Electronic Speculum.
Specific embodiment
Embodiment 1
A) carry out vacuum magnetic-control sputtering nickel plating to polyurethane sponge: selection aperture is 110PPI, with a thickness of the poly- ammonia of 1.4mm
Ester foam, polyurethane foam is mounted on magnetron sputtering apparatus, vacuum chamber is closed, as background vacuum≤0.11Pa
When, enter the tape transport sputtering stage after opening target power supply 4min, adjust target power output and argon flow, opens waterway circulating valve to reduce
Target temperature prevents polyurethane sponge from gasifying or deforming at high temperature, opens sputtering target power supply and is sputtered, sputtering target is rectangular
Nickel target, tape running speed 7m/min is 0.9Pa, sputters 3 under target power output 2.5kW, argon flow 80sccm in working vacuum degree
Time, then it is 0.4Pa, sputtered 1 time under target power output 3.5kW, argon flow 120sccm in working vacuum degree, entirely sputtered
Journey terminates, and first closes target power supply, is then shut off shielding power supply, then stops vacuumizing, finally turns off waterway circulating valve；
B) will by step a) treated conductive polyurethane sponge in the electroplate liquid that pH is 0-1 electrotinning, electroplate liquid
Component are as follows: the content of tin methane sulfonate is 30g/L, and the content of methane sulfonic acid is 160ml/L, the content of S-1028 open cylinder agent A
For 60ml/L, the content of S-1028 brightener B is 10ml/L, the condition of plating are as follows: electroplating current 20A, electroplating current density
For 2.4A/dm2, electroplating temperature is 20 DEG C, and after 60min is electroplated, foam tin material is obtained after washing and drying.
Embodiment 2
A) carry out vacuum magnetic-control sputtering nickel plating to polyurethane sponge: selection aperture is 140PPI, with a thickness of the poly- ammonia of 0.9mm
Ester foam, polyurethane foam is mounted on magnetron sputtering apparatus, vacuum chamber is closed, as background vacuum≤0.11Pa
When, enter the tape transport sputtering stage after opening target power supply 5min, adjust target power output and argon flow, opens waterway circulating valve to reduce
Target temperature prevents polyurethane sponge from gasifying or deforming at high temperature, opens sputtering target power supply and is sputtered, sputtering target is rectangular
Nickel target, tape running speed 6.0m/min is 0.8Pa, splashes under target power output 2.8kW, argon flow 90sccm in working vacuum degree
It penetrates 1 time, is then 0.3Pa, is sputtered 3 times under target power output 4.0kW, argon flow 140sccm in working vacuum degree, it is entire to sputter
Process terminates, and first closes target power supply, is then shut off shielding power supply, then stops vacuumizing, finally turns off waterway circulating valve；
B) will by step a) treated conductive polyurethane sponge in the electroplate liquid that pH is 0-1 electrotinning, electroplate liquid
Component are as follows: the content of tin methane sulfonate is 50g/L, and the content of methane sulfonic acid is 120ml/L, the content of S-1028 open cylinder agent A
For 80ml/L, the content of S-1028 brightener B is 15ml/L, the condition of plating are as follows: electroplating current 20A, electroplating current density
For 2.4A/dm2, electroplating temperature is 25 DEG C, and after 60min is electroplated, foam tin material is obtained after washing and drying.
Embodiment 3
A) carry out vacuum magnetic-control sputtering nickel plating to polyurethane sponge: selection aperture is 80PPI, with a thickness of the polyurethane of 4mm
Polyurethane foam is mounted on magnetron sputtering apparatus by foam, vacuum chamber is closed, as background vacuum≤0.11Pa
When, enter the tape transport sputtering stage after opening target power supply 8min, adjust target power output and argon flow, opens waterway circulating valve to reduce
Target temperature prevents polyurethane sponge from gasifying or deforming at high temperature, opens sputtering target power supply and is sputtered, sputtering target is rectangular
Nickel target, tape running speed 4.0m/min is 0.3Pa, splashes under target power output 3.0kW, argon flow 120sccm in working vacuum degree
It penetrates 3 times, is then 0.4Pa, is sputtered 4 times under target power output 4.5kW, argon flow 160sccm in working vacuum degree, it is entire to sputter
Process terminates, and first closes target power supply, is then shut off shielding power supply, then stops vacuumizing, finally turns off waterway circulating valve；
B) will by step a) treated conductive polyurethane sponge in the electroplate liquid that pH is 0-1 electrotinning, electroplate liquid
Component are as follows: the content of tin methane sulfonate is 20g/L, and the content of methane sulfonic acid is 180ml/L, the content of S-1028 open cylinder agent A
For 100ml/L, the content of S-1028 brightener B is 12ml/L, the condition of plating are as follows: electroplating current 20A, electroplating current density
For 2.4A/dm2, electroplating temperature is 20 DEG C, and after 60min is electroplated, foam tin material is obtained after washing and drying.
Comparative example 1
A) carry out vacuum magnetic-control sputtering nickel plating to polyurethane sponge: selection aperture is 80PPI, with a thickness of the polyurethane of 4mm
Polyurethane foam is mounted on magnetron sputtering apparatus by foam, vacuum chamber is closed, as background vacuum≤0.11Pa
When, enter the tape transport sputtering stage after opening target power supply 8min, adjust target power output and argon flow, opens waterway circulating valve to reduce
Target temperature prevents polyurethane sponge from gasifying or deforming at high temperature, opens sputtering target power supply and is sputtered, sputtering target is rectangular
Nickel target, tape running speed 4.0m/min is 0.4Pa, splashes under target power output 4.5kW, argon flow 160sccm in working vacuum degree
It penetrates 7 times, entire sputtering process terminates, and first closes target power supply, is then shut off shielding power supply, then stops vacuumizing, finally close again
Close waterway circulating valve；
B) will by step a) treated conductive polyurethane sponge in the electroplate liquid that pH is 0-1 electrotinning, electroplate liquid
Component are as follows: the content of tin methane sulfonate is 20g/L, and the content of methane sulfonic acid is 180ml/L, the content of S-1028 open cylinder agent A
For 100ml/L, the content of S-1028 brightener B is 12ml/L, the condition of plating are as follows: electroplating current 20A, electroplating current density
For 2.4A/dm2, electroplating temperature is 20 DEG C, and after 60min is electroplated, foam tin material is obtained after washing and drying.
Comparative example 2
A) carry out vacuum magnetic-control sputtering chromium plating to polyurethane sponge: selection aperture is 80PPI, with a thickness of the polyurethane of 4mm
Polyurethane foam is mounted on magnetron sputtering apparatus by foam, vacuum chamber is closed, as background vacuum≤0.11Pa
When, enter the tape transport sputtering stage after opening target power supply 8min, adjust target power output and argon flow, opens waterway circulating valve to reduce
Target temperature prevents polyurethane sponge from gasifying or deforming at high temperature, opens sputtering target power supply and is sputtered, sputtering target is cylinder
Tubular chromium target, tape running speed 6.0m/min, working vacuum degree be 0.2Pa, target power output 3.0kW, argon flow 130sccm
Lower sputtering 2 times, is then 0.4Pa, sputters 3 times under target power output 4.2kW, argon flow 150sccm, entirely in working vacuum degree
Sputtering process terminates, and first closes sputtering target power supply, closes bias valve, then stops vacuumizing, and finally continues 300s again and is filled with argon gas；
B) will by step a) treated conductive polyurethane sponge in the electroplate liquid that pH is 0-1 electrotinning, electroplate liquid
Component are as follows: the content of tin methane sulfonate is 20g/L, and the content of methane sulfonic acid is 180ml/L, and the content of additive A is
100ml/L, the content of additive B are 12ml/L, the condition of plating are as follows: electroplating current 20A, electroplating current density 2.4A/
dm2, electroplating temperature is 20 DEG C, and after 60min is electroplated, foam tin material is obtained after washing and drying.
Comparative example 3
A) carry out vacuum magnetic-control sputtering nickel plating to polyurethane sponge: selection aperture is 80PPI, with a thickness of the polyurethane of 4mm
Polyurethane foam is mounted on magnetron sputtering apparatus by foam, vacuum chamber is closed, as background vacuum≤0.11Pa
When, enter the tape transport sputtering stage after opening target power supply 8min, adjust target power output and argon flow, opens waterway circulating valve to reduce
Target temperature prevents polyurethane sponge from gasifying or deforming at high temperature, opens sputtering target power supply and is sputtered, sputtering target is rectangular
Nickel target, tape running speed 4.0m/min is 0.3Pa, splashes under target power output 3.0kW, argon flow 120sccm in working vacuum degree
It penetrates 3 times, is then 0.4Pa, is sputtered 4 times under target power output 4.5kW, argon flow 160sccm in working vacuum degree, it is entire to sputter
Process terminates, and first closes target power supply, is then shut off shielding power supply, then stops vacuumizing, finally turns off waterway circulating valve；
B) will by step a) treated conductive polyurethane sponge in the electroplate liquid that pH is 0-1 electrotinning, electroplate liquid
Component are as follows: the content of tin methane sulfonate is 20g/L, and the content of methane sulfonic acid is 180ml/L, the condition of plating are as follows: plating electricity
Stream is 20A, electroplating current density 2.4A/dm2, electroplating temperature is 20 DEG C, and after 60min is electroplated, foam is obtained after washing and drying
Tin material.
Comparative example 4
Method disclosed in background technique using number of patent application CN201010189543.4 prepares foam tin material.
The foam tin material that embodiment 2 is obtained is with SEM/EDS (scanning electron microscope) energy spectrum analysis in foam tin material
Each metal element content is analyzed.
Wherein, SEM (scanning electron microscope): scanning electron microscope, EDS (Energy
Dispers ive Spectrometer): X-ray micro-zone analysis.
The present invention is tested using the scanning electron microscope of Japan Electronics scanning electron microscope JSM-IT300 model, have SEM and
EDS analytic function.
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) that foam tin material amplifies 200 times, and Fig. 2 is that foam tin material amplifies 2000 times
Scanning electron microscope (SEM) photograph.Fig. 3 is the scanning electron microscope (SEM) photograph that foam tin material amplifies 300 times, finds foam tin rib fracture (Fig. 3 on the diagram
It is middle with box outline come position), then incision position carry out EDS detect ingredient, obtain EDS test result as shown in Figure 4
The ingredient list of figure, EDS test output is as shown in table 1.
The mass percentage of each metallic element of table 1
| Element | Mass percentage (%) |
| Al | 0.23 |
| Mo | 0.07 |
| Sn | 99.70 |
| Total amount: | 100.00 |
Tin can form fine and close crystal layer on the surface of polyurethane sponge it can be seen from SEM.Foam is detected by EDS
The mass percentage that the mass percentage that the mass percentage of the Sn of tin material is 99.7%, Al is 0.23%, Mo is
0.07%, the content of nickel element is not detected, illustrates that its content is extremely low, a small amount of Al and Mo are to bring into electro-deposition process of tin
's.Thus illustrate, the content of tin is high in the foam tin material obtained using the present processes, and impurity is less, is not detected
The content of nickel.
Fig. 5 is the foam tin crystalline substance wall thickness that foam tin material is measured by scanning electron microscope, test method are as follows: passes through scanning electricity
After mirror JSM-IT300 shoots the cross section of foam tin material rib fracture at photo, by the artificial gauge length of software in Electronic Speculum, survey
Rib wall thickness is measured, method multiple is 800, and the metal layer thickness finally measured is 11-14 μm, and the wall layer thickness of rib is uniform.
The performance of foam tin material obtained by embodiment 1-3 and comparative example 1-4 is relatively shown in Table 1.
Wherein foam tin material squeezes the test method of resilience performance are as follows: foam tin material is squeezed into 0.4mm thickness, then
Its thickness after 1 hour is surveyed, its rebounding ratio is calculated.
The test method of the tension maximum, force of foam tin material are as follows: the sample block that foam tin material is cut into 15cm*2cm exists
It stretches and carries out tensile strength test on instrument, record its tension maximum, force and tension elongation.
The performance of 1 foam tin material of table
Data can be seen that the foam tin material obtained using the present processes from upper table, compared to comparative example
Method obtains foam tin material, and tension maximum, force and rebounding ratio are all higher, has excellent performance, long service life, foam tin material
Show that there is good elongation percentage and crushing resistance when stress and compression, under a certain range of stress, compression environment
Its three-dimensional porous structure is not changed, rib keeps integrality not broken.Illustrate to use the present processes with vacuum magnetic-control sputtering
Technology nickel plating on polyurethane sponge, then re-plating tin, entire simple process, and polyurethane sponge needs not move through roughening
Equal pre-treatments, energy conservation and environmental protection, and can be carried out extensive consecutive production, finally obtained foam tin material is examined by SEM/EDS
Survey, the content of nickel is not detected, illustrates that its content is extremely low, the content of tin has reached 99.7%, compared to the prior art, tin it is pure
Degree greatly improves, and the performance of corresponding foam tin also gets a promotion.In addition it can illustrate from the data in comparative example 3, only adopt
With the electroplate liquid electrotinning of the application, and combined with above-mentioned vacuum magnetic-control sputtering nickel plating technology, obtained foam tin material
It has excellent performance, long service life, foam tin material shows the elongation percentage and resistance to compression that have excellent when stress and compression
Property.
Claims (9)
1. a kind of preparation method of foam tin material, which is characterized in that include the following steps:
A) vacuum magnetic-control sputtering nickel plating is carried out to polyurethane sponge；
B) foam tin will be obtained after washing and drying by step a) treated conductive polyurethane sponge electrotinning in electroplate liquid
Material.
2. the preparation method of foam metal shielding material as described in claim 1, which is characterized in that poly- ammonia described in step a)
Ester sponge with a thickness of 0.5-5mm.
3. the preparation method of foam tin material as described in claim 1, which is characterized in that vacuum magnetic-control sputtering described in step a)
The process conditions of nickel plating are as follows: background vacuum≤0.11pa, working vacuum degree 0.3-0.9Pa, polyurethane sponge walking speed are 4-7m/
Min, argon flow 80-180sccm.
4. the preparation method of foam tin material as claimed in claim 1 or 2, which is characterized in that vacuum magnetic control described in step a)
The concrete operations of sputtering nickel plating are: vacuumizing, as background vacuum≤0.11Pa, enter tape transport after opening target power supply 2-8min
The sputtering stage adjusts target power output and argon flow, opens waterway circulating valve, opens sputtering target power supply and is sputtered, and work is true
Reciprocal of duty cycle control is 0.3-0.9Pa, and target power output control sputters 1- by sputtering target in 2.5-3.0KW, argon flow 80-120sccm
3 times, then working vacuum degree is controlled as 0.3-0.4Pa, target power output is controlled at 3.5-4.5KW, argon flow 120-180sccm
Then sputtering 1-4 times stops sputtering.
5. the preparation method of foam tin material as claimed in claim 4, which is characterized in that the material of the sputtering target is metal
Nickel.
6. the preparation method of foam tin material as claimed in claim 1 or 2, which is characterized in that electroplate liquid described in step b)
Component are as follows: tin methane sulfonate, methane sulfonic acid, additive A, additive B and water.
7. the preparation method of foam tin material as claimed in claim 6, which is characterized in that tin methane sulfonate in the electroplate liquid
Content is 20-50g/L, and the content of methane sulfonic acid is 120-180ml/L, and the content of additive A is 60-100ml/L, additive B
Content be 10-15ml/L.
8. the preparation method of foam tin material as claimed in claim 1 or 2, which is characterized in that the work of plating described in step b)
Skill condition are as follows: electroplating current 20A, electroplating current density 2.4A/dm2, electroplating temperature is 20-25 DEG C.
9. the preparation method of foam tin material as described in claim any one of 1-3, which is characterized in that polyurethane after the plating
The surface density of sponge outer layer metal tin is 400-600g/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811300505.4A CN109267024B (en) | 2018-11-02 | 2018-11-02 | Preparation method of foam tin material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811300505.4A CN109267024B (en) | 2018-11-02 | 2018-11-02 | Preparation method of foam tin material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109267024A true CN109267024A (en) | 2019-01-25 |
| CN109267024B CN109267024B (en) | 2020-11-20 |
Family
ID=65191202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811300505.4A Active CN109267024B (en) | 2018-11-02 | 2018-11-02 | Preparation method of foam tin material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109267024B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003681A (en) * | 2019-04-02 | 2019-07-12 | 柳州光华科技有限公司 | A kind of preparation method of foam tin material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392082A2 (en) * | 1989-04-14 | 1990-10-17 | Katayama Special Industries, Ltd. | Method for manufacturing a metallic porous sheet |
| CN1392293A (en) * | 2001-06-14 | 2003-01-22 | 长沙力元新材料股份有限公司 | Foam iron alloy material, foam iron base composite material and their preparing method |
| CN101824619A (en) * | 2010-06-01 | 2010-09-08 | 武汉银泰科技电源股份有限公司 | Preparation method of foam tin material |
| CN102212791A (en) * | 2011-06-02 | 2011-10-12 | 爱蓝天高新技术材料(大连)有限公司 | Equipment and method for performing magnetron-controlled sputter coating on polyester type polyurethane foam matrix |
| CN103882484A (en) * | 2014-04-04 | 2014-06-25 | 哈尔滨工业大学 | Plating solution for high-speed electrotinning |
-
2018
- 2018-11-02 CN CN201811300505.4A patent/CN109267024B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0392082A2 (en) * | 1989-04-14 | 1990-10-17 | Katayama Special Industries, Ltd. | Method for manufacturing a metallic porous sheet |
| CN1392293A (en) * | 2001-06-14 | 2003-01-22 | 长沙力元新材料股份有限公司 | Foam iron alloy material, foam iron base composite material and their preparing method |
| CN101824619A (en) * | 2010-06-01 | 2010-09-08 | 武汉银泰科技电源股份有限公司 | Preparation method of foam tin material |
| CN102212791A (en) * | 2011-06-02 | 2011-10-12 | 爱蓝天高新技术材料(大连)有限公司 | Equipment and method for performing magnetron-controlled sputter coating on polyester type polyurethane foam matrix |
| CN103882484A (en) * | 2014-04-04 | 2014-06-25 | 哈尔滨工业大学 | Plating solution for high-speed electrotinning |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003681A (en) * | 2019-04-02 | 2019-07-12 | 柳州光华科技有限公司 | A kind of preparation method of foam tin material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109267024B (en) | 2020-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Silva et al. | Electrodeposition of Cu–Zn alloy coatings from citrate baths containing benzotriazole and cysteine as additives | |
| Ibrahim et al. | Role of glycine as a complexing agent in nickel electrodeposition from acidic sulphate bath | |
| CN110016700B (en) | Surface-enhanced Raman spectrum silver-plated active substrate and preparation method thereof | |
| Kim et al. | Pulse plating effects in nickel electrodeposition | |
| Zhang et al. | Electrodeposit copper from alkaline cyanide-free baths containing 5, 5′-dimethylhydantoin and citrate as complexing agents | |
| CN109267024A (en) | A kind of preparation method of foam tin material | |
| CN101008095B (en) | Pulse silver-coating method | |
| Zaabar et al. | Influence of nettle extract on zinc electrodeposition in an acidic bath: Electrochemical effect and coating morphology | |
| Wang et al. | Investigation of C/Al–Cr–N multilayer coatings for stainless steel bipolar plate in polymer electrolyte membrane fuel cells | |
| US6875324B2 (en) | Sputtering target material | |
| Moniruzzaman et al. | Fe-Ni alloy electrodeposition from simple and complex type sulfate electrolytes containing Ni/Fe ratio of 1 and 12 | |
| CN106350058A (en) | Preparation method of nanoporous gold-based fluorescence enhanced base | |
| CN1966779A (en) | Process for making Ni-Cu-Ag multilayer film | |
| CN109750283A (en) | A kind of process of SMC material chemical plating nickel-phosphorus alloy on surface | |
| Assaf et al. | Electroplating of brass from citrate-based alloy baths | |
| CN112359357B (en) | Chemical nickel plating process for steel sheet, phosphorus-nickel plated steel sheet and uniform temperature plate | |
| Yang et al. | Electrodeposition of Ni–Co alloy films onto titanium substrate | |
| Srivastava et al. | A study of the effects of surfactants on the electrodeposition of Ni Co alloy | |
| CN101734863A (en) | Ternary manganese nitride Mn3CuN thin film with trans-perovskite structure | |
| CN100408713C (en) | Binary NiP amorphous alloy bulk and method for preparing same | |
| Wang et al. | Influence of 2-butyne-1, 4-diol on the structure and performance of the Co-Ni alloy plated by electrodeposition | |
| JP3436763B2 (en) | Sputtering target material | |
| WO2024016268A1 (en) | High-entropy alloy electrode and preparation method therefor, gas sensor, and use thereof | |
| Li et al. | Effect of Copper Ion Concentration on Microstructure and Mechanical Properties of Electrolytic Copper Foil | |
| Rosley et al. | Effect of Current Densities in Cu-Sn-Zn Electroplating Process on Carbon Substrate Using Less Hazardous Electrolyte |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |