CN104674199A - Method for performing palladium-free activation electroless copper plating on basalt fiber - Google Patents
Method for performing palladium-free activation electroless copper plating on basalt fiber Download PDFInfo
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- CN104674199A CN104674199A CN201510072816.XA CN201510072816A CN104674199A CN 104674199 A CN104674199 A CN 104674199A CN 201510072816 A CN201510072816 A CN 201510072816A CN 104674199 A CN104674199 A CN 104674199A
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Abstract
The invention relates to a method for performing palladium-free activation electroless copper plating on a basalt fiber. The method comprises the following steps: removing the impurities on the surface of the basalt fiber by an organic solvent, etching by using the sodium hydroxide, performing palladium-free activation on the basalt fiber, plating a metallic copper on the surface of the basalt fiber through an electroless copper plating method by taking the glyoxylic acid as a reducing agent to obtain the copperized basalt fiber. The method of the copperized basalt fiber is simple in process, low in cost, high in production efficiency, good in plating binding force and facilitates batch production and control on the shape and the size of the pattern of the conductive plating; and the basalt fiber prepared by the method is good in conductive effect, and the binding fastness of the metal coating and the basalt fiber is good.
Description
Technical field
The invention belongs to the function coating field of basalt fibre, more particularly, relate to a kind of method of basalt fibre no-palladium activating electroless copper.
Background technology
Basalt fibre is as a kind of high-performance fiber, there is good mechanical property as comparatively high-tensile and Young's modulus owing to having basalt fibre, also has excellent physico performance simultaneously, as good binding property, thermotolerance, uninflammability and erosion resistance etc., and basalt fibre is prepared pollution-free, be parent soil material excellent specific property after degraded, be widely used in military project and the civil areas such as aerospace, building, chemical industry, medical science, electronics, agricultural.Because basalt fibre is non-conductive, to the unshielded ability of hertzian wave, makes it apply and be subject to a definite limitation.If layer of metal can be plated in its surface, improve its surface property, will be widened it and apply at electronic applications, and can be used as electro-conductive material and electromagnetic shielding material.At present both at home and abroad about the method for weaving face fabric surface metalation process has vacuum deposition method, magnetron sputtering method, plating and electroless plating method etc.Wherein chemical plating technology due to its required equipment is simple, cost is low and the coating obtained and basal body binding force good, be applicable to the advantages such as scale operation and be widely used in non-metal material surface metalized.Fabric metal lining mainly contains nickel, copper, silver and composite deposite thereof.Copper is owing to having good electroconductibility, thermal conductivity, ductility, and advantages such as low price and become study hotspot.
The prerequisite of electroless plating is that substrate surface to be plated has catalytic activity, because textile fibres itself is inert material, need before plating to carry out activating pretreatment, make its surface adsorption last layer can cause the catalyzer of electroless plating, usual employing precious metal palladium is as activator, though the method can obtain metal plating, desired raw material cost is high.The present invention seeks to adopt no-palladium activating electroless copper to obtain conduction basalt fibre.
Summary of the invention
The technical problem to be solved in the present invention is, there is provided chemical-copper-plating process condition to make copper be plated to the method on basalt fibre surface, the method technique is simple, and cost is low, uniform conducting function coating can be formed on basalt fibre surface, keep the comfortableness of basalt fibre simultaneously.
Technical scheme of the present invention: first pre-treatment is carried out to basalt fibre surface, organic solvent is utilized to remove the impurity on basalt fibre surface, sodium hydroxide is adopted to etch basalt fibre again, then copper sulfate-sodium borohydride solution is adopted to activate, finally electroless copper is carried out to basalt fibre, its feature is, on basalt fibre, to form copper coating by chemical plating method on basalt fibre.
The invention provides a kind of basalt fibre no-palladium activating electroless copper plating method, its raw material comprises copper sulfate, disodium ethylene diamine tetraacetate, yellow prussiate of potash, oxoethanoic acid, sodium hydroxide, ethanol, acetone and basalt fibre fabrics.
Described activator is at least one in copper sulfate-sodium borohydride, cupric chloride-sodium borohydride, single nickel salt-sodium borohydride, cupric chloride-sodium borohydride, Silver Nitrate, Palladous chloride.
The technical solution adopted for the present invention to solve the technical problems is: a kind of basalt fibre no-palladium activating electroless copper plating method, is characterized in that, comprise the following steps:
S1: basalt fibre is used dehydrated alcohol, acetone and washed with de-ionized water successively, then dry 1-3h at 70 DEG C of-90 DEG C of temperature, to remove unnecessary moisture.
S2: by the copper-bath room temperature activation treatment 3-60min of described basalt fibre 5-30g/l, takes out and to put it in 2-30g/l sodium borohydride solution after room temperature treatment 1-60min, take out for subsequent use, at the dry 0.5-3h of room temperature-90 DEG C.
S3: carry out electroless copper to the basalt fibre after activation, metallic copper is plated to basalt fibre surface, by washed with de-ionized water, dries at 50-90 DEG C.
Preferably, organic solvent described in step S1 is acetone and ethanol, and its volume ratio is 1 ~ 3:1, supersound process 30-180min.
Can carry out the pre-treatment of 10-80g/l sodium hydroxide etching to basalt fibre after described S1, etching temperature: room temperature-80 DEG C, etching time: 30-180min, uses washed with de-ionized water.
Preferably, in step S3, in preparation method according to conduction basalt fibre of the present invention, chemical plating technology condition is: 11-23g/l copper sulfate, 10-40g/l disodium ethylene diamine tetraacetate, 6-21g/l oxoethanoic acid, 0-3.0ml yellow prussiate of potash (0.1-0.5 g/l), pH is 10.5-12.5, and temperature is 55-80 DEG C.Under above-mentioned parameter condition, electroless plating time is: 10-60min.
Implement the method for no-palladium activating electroless copper legal system of the present invention standby conduction basalt fibre, there is following beneficial effect: the present invention adopts electroless plating technology, have the advantages that production efficiency is high, cost is low, simple process, coating binding force are good, reproducible, be easy to batch production, and the electroless copper basalt fibre obtained has conducting function.
accompanying drawing illustrates:
Fig. 1 is that basalt fibre fabrics electroless copper SEM prepared by the embodiment of the present invention 1 schemes (amplifying 3000 times)
Fig. 2 is that basalt fibre fabrics electroless copper SEM prepared by the embodiment of the present invention 1 schemes (amplifying 30000 times)
Fig. 3 is basalt fibre fabrics electroless copper XRD figure prepared by the embodiment of the present invention 1
Fig. 4 is the contact angle of basalt fibre fabrics of the present invention
Fig. 5 is the basalt fibre fabrics contact angle after NaOH etching prepared by the embodiment of the present invention 2
Fig. 6 is that the basalt fibre fabrics electroless copper SEM that the embodiment of the present invention 2 is prepared after NaOH etching schemes (amplifying 3000 times)
Fig. 7 is that the basalt fibre fabrics electroless copper SEM that the embodiment of the present invention 2 is prepared after NaOH etching schemes (amplifying 30000 times).
Embodiment
The invention provides a kind of basalt fibre without palladium electroless copper plating method, its raw material comprises copper sulfate, disodium ethylene diamine tetraacetate, yellow prussiate of potash, oxoethanoic acid, sodium hydroxide, ethanol, acetone and basalt fibre.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method method of basalt fibre no-palladium activating electroless copper, is characterized in that, comprise the following steps:
S1: basalt fibre is used dehydrated alcohol, acetone and washed with de-ionized water successively, then dry 1-3h at 70 DEG C of-90 DEG C of temperature, to remove unnecessary moisture.
S2: by the copper-bath room temperature activation treatment 3-60min of described basalt fibre 5-30g/l, takes out and to put it in 2-30g/l sodium borohydride solution after room temperature treatment 1-60min, take out for subsequent use, at the dry 0.5-3h of room temperature-90 DEG C.
S3: carry out electroless copper to the basalt fibre after activation, metallic copper is plated to basalt fibre surface, by washed with de-ionized water, dries at 50-90 DEG C.
Preferably, organic solvent described in step S1 is acetone and ethanol, and its volume ratio is 1 ~ 3:1, supersound process 30-180min.
Can carry out the pre-treatment of 10-80g/l sodium hydroxide etching to basalt fibre after described S1, etching temperature: room temperature-80 DEG C, etching time: 30-180min, uses washed with de-ionized water.
Preferably, in step S3, according in the method for basalt fibre of the present invention without palladium electroless copper, chemical plating technology condition is: 11-23g/l copper sulfate, 10-40g/l disodium ethylene diamine tetraacetate, 6-21g/l oxoethanoic acid, 0-3.0ml yellow prussiate of potash (0.1-0.5 g/l), pH is 10.5-12.5, and temperature is 55-80 DEG C.Under above-mentioned parameter condition, electroless plating time is: 10-60min.
Below in conjunction with embodiment, the present invention is further illustrated.
embodiment 1the basalt fibre fabrics acetone and ethanol (1:1) mixed solution that are of a size of 5cm × 5cm are cleaned 30min in 50 DEG C of water-baths, takes out fabric and dry in an oven.Fabric after cleaning is placed in activation treatment 3min in 5g/l copper-bath, takes out textile impregnation and process 3min in 5g/l sodium borohydride solution.Cloth specimen after activation puts into chemical copper plating solution, and plating solution is by 20g/l CuSO
4, 20g/l disodium ethylene diamine tetraacetate, 18g/l oxoethanoic acid, 2.5ml 0.2 g/l yellow prussiate of potash forms, and pH value is 12.0, and bath temperature is 70 DEG C, takes out cloth specimen after copper facing 30min, cools rear washed with de-ionized water a little, dries in 80 DEG C of baking ovens.
The micro-structure and property performance of conduction basalt fabric is as follows:
1, the surface topography of conduction copper facing basalt fabric:
The stereoscan photograph of electroless copper basalt fabric under different amplification is shown in Fig. 1 and 2.As seen from the figure, basalt fibre surface is covered by copper particle completely, and copper particle is uniform plating at fabric face.Be the SEM of 30000 from magnification, copper particle has been united phenomenon, and the particle size after uniting is that copper nano particles is spherical in shape, and particle diameter is about 60-100nm, even particle size distribution.
2, the crystalline structure of conduction copper facing basalt fabric:
The crystalline structure of basalt fabric electroless copper is shown in Fig. 3.According to X-ray diffraction standard card PDF, can determine that copper facing coating is face-centred cubic crystalline structure by diffraction peak data, the diffraction peaks being 43.28 °, 50.43 °, 74.13 °, 89.84 ° places at 2 θ represent the crystal face of (111), (200), (220) and (311) of copper respectively, do not occur the diffraction peak of cupric oxide in XRD figure spectrum, result shows the layers of copper mainly metallic copper in electroless copper basalt fabric.
3, the conductivity of copper facing basalt fabric:
Table 1 is the surface resistivity comparison sheet of basalt fabric and copper facing basalt fabric.Surface resistivity is lower, show that electroconductibility is better, the surface resistivity of the original cloth specimen of basalt fabric is infinitely great, explanation basalt fabric is non-conductive, after electroless copper process, the surface resistivity of basalt fabric reduces to 78.3 m Ω/sq, shows that electroless copper basalt fabric has higher electroconductibility.
Surface resistivity after the original basalt fibre fabrics of table 1 and electroless copper
| Sample | Basalt fabric | Electroless copper basalt fabric |
| Resistance (m Ω/sq) | Infinitely great | 57.50 |
embodiment 2the basalt fibre fabrics acetone and ethanol (1:1) mixed solution that are of a size of 5cm × 5cm are cleaned 30min in 50 DEG C of water-baths, takes out fabric and dry in an oven.The fabric of wash clean is put into 10g/l, difference normal temperature process 30min in the NaOH solution of 20g/l and 40g/l, then taking-up washed with de-ionized water is dried.Fabric after etching is put into 5g/l copper-bath activation treatment 3min, is immersed in after taking-up in 5g/l sodium borohydride solution and processes 3min.Fabric after activation puts into chemical copper plating solution, and plating solution is by 20g/l CuSO
4, 20g/l disodium ethylene diamine tetraacetate, 18g/l oxoethanoic acid, 2.5ml 0.2 g/l yellow prussiate of potash forms, and pH value is 12.0, and bath temperature is 70 DEG C, takes out fabric after copper facing 30min, cools rear washed with de-ionized water a little, dries in 80 DEG C of baking ovens.
The micro-structure and property performance of conduction basalt fabric is as follows:
1. the basalt fabric contact angle after NaOH pre-treatment:
The contact angle of basalt fabric before and after NaOH etching processing is shown in Fig. 4 and 5, as seen from the figure, original basalt fabric contact angle is 95.62 °, after etching, basalt fabric contact angle is 39.86 °, result shows that basalt fabric refuses water, after NaOH etching, contact angle reduces, and illustrates that fabric hydrophilic performance increases, is conducive to nickel deposition on the surface of the fabric.
2. the surface topography of conduction copper facing basalt fibre fabrics:
Stereoscan photograph after basalt fabric electroless copper after the NaOH etching of 40g/l under different amplification is shown in Fig. 6 and 7.As seen from the figure, basalt fabric surface is covered by copper particle completely, and copper particle is uniform plating at fabric face.Be the SEM of 30000 from magnification, copper even particle distribution degree is higher than the copper particle etched without NaOH on the fabric of pre-treatment, copper particle unites phenomenon than the basalt fabric electroless copper without NaOH pre-treatment more seriously, and particle diameter is about 150-200nm.
3, the conductivity of copper facing basalt fibre fabrics:
Table 2 is the copper-plated surface resistivity of basalt fibre fabrics behind the front place of NaOH, and with the increase of NaOH concentration, the resistance of copper facing basalt fibre fabrics first reduces rear increase.When NaOH concentration is 40g/l, the resistance of basalt fibre fabrics reaches 78.3 m Ω/sq.
Table 2 different concns NaOH pre-treatment is on the impact of basalt fibre fabrics surface resistivity
。
Claims (9)
1. a conduction basalt fibre, comprise basalt fibre and metal level, it is characterized in that described substrate is basalt fibre, described conductive layer is coating material with metal, utilizes chemical plating method to form metal plating on basalt fibre.
2. conduction basalt fibre according to claim 1, is characterized in that, described electro-conductive material is metallic copper.
3. conduction basalt fibre according to claim 2, is characterized in that, prepared by described metal plating chemical plating method.
4. in electroless plating according to claim 3, it is characterized in that, adopt no-palladium activating legal system for metal copper facing basalt fibre.
5. in electroless plating according to claim 3, it is characterized in that, chemical plating solution does not adopt poisonous formaldehyde, and with oxoethanoic acid as reductive agent.
6. a basalt fibre is characterized in that without the method for palladium electroless copper, comprises step:
S1: basalt fibre is used dehydrated alcohol, acetone and washed with de-ionized water successively, then dry 1-3h at 70 DEG C of-90 DEG C of temperature, to remove unnecessary moisture;
S2: by the copper-bath room temperature activation treatment 3-60min of described basalt fibre 5-30g/l, takes out and to put it in 2-30g/l sodium borohydride solution after room temperature treatment 1-60min, take out for subsequent use, at the dry 0.5-3h of room temperature-90 DEG C;
S3: carry out electroless copper to the basalt fibre after activation, metallic copper is plated to basalt fibre surface, by washed with de-ionized water, dries at 50-90 DEG C.
7. the preparation method of conduction basalt fibre according to claim 5, it is characterized in that, the pre-treatment of 10-80g/l sodium hydroxide etching can be carried out, etching temperature: room temperature-80 DEG C by basalt fibre after described S1, etching time: 30-180min, uses washed with de-ionized water.
8. the preparation method of conduction basalt fibre according to claim 5, it is characterized in that, in described step S3, described chemical-copper-plating process condition is: 11-23g/l copper sulfate, 10-40g/l disodium ethylene diamine tetraacetate, 6-21g/l oxoethanoic acid, 0-3.0ml yellow prussiate of potash (0.1-0.5 g/l), pH is 10.5-12.5, and temperature is 55-80 DEG C.
9., under above-mentioned parameter condition, electroless plating time is: 10-60min.
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| CN201510072816.XA CN104674199A (en) | 2015-02-12 | 2015-02-12 | Method for performing palladium-free activation electroless copper plating on basalt fiber |
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| CN201510072816.XA CN104674199A (en) | 2015-02-12 | 2015-02-12 | Method for performing palladium-free activation electroless copper plating on basalt fiber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200761A (en) * | 2015-10-13 | 2015-12-30 | 四川大学 | Palladium-free activation chemical nickel-plating method for electromagnetic shielding polyphenylene sulfide fiber |
| CN108218216A (en) * | 2018-02-09 | 2018-06-29 | 中国科学院新疆理化技术研究所 | A kind of preparation method of conduction basalt fiber material |
| CN114107963A (en) * | 2021-10-26 | 2022-03-01 | 重庆智笃新材料科技有限公司 | Basalt fiber continuous chemical plating device and application method |
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| JP2001107258A (en) * | 1999-10-06 | 2001-04-17 | Hitachi Ltd | Electroless copper plating method, plating device and multilayer wiring board |
| CN103060779A (en) * | 2012-12-04 | 2013-04-24 | 复旦大学 | Preparation method of copper/modal fiber composite material |
| CN103388113A (en) * | 2013-07-25 | 2013-11-13 | 辽宁工程技术大学 | Basalt fiber reinforced magnesium alloy composite material and preparation method thereof |
| CN103540915A (en) * | 2013-11-12 | 2014-01-29 | 哈尔滨理工大学 | Method for chemically plating polyimide surface with copper |
| CN103805971A (en) * | 2014-03-11 | 2014-05-21 | 东华大学 | Method for activating electroless copper-plated textile with nickel salt |
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2015
- 2015-02-12 CN CN201510072816.XA patent/CN104674199A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001107258A (en) * | 1999-10-06 | 2001-04-17 | Hitachi Ltd | Electroless copper plating method, plating device and multilayer wiring board |
| CN103060779A (en) * | 2012-12-04 | 2013-04-24 | 复旦大学 | Preparation method of copper/modal fiber composite material |
| CN103388113A (en) * | 2013-07-25 | 2013-11-13 | 辽宁工程技术大学 | Basalt fiber reinforced magnesium alloy composite material and preparation method thereof |
| CN103540915A (en) * | 2013-11-12 | 2014-01-29 | 哈尔滨理工大学 | Method for chemically plating polyimide surface with copper |
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Non-Patent Citations (1)
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| 张允诚等: "《电镀手册》", 31 December 2011 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200761A (en) * | 2015-10-13 | 2015-12-30 | 四川大学 | Palladium-free activation chemical nickel-plating method for electromagnetic shielding polyphenylene sulfide fiber |
| CN108218216A (en) * | 2018-02-09 | 2018-06-29 | 中国科学院新疆理化技术研究所 | A kind of preparation method of conduction basalt fiber material |
| CN108218216B (en) * | 2018-02-09 | 2020-12-25 | 中国科学院新疆理化技术研究所 | Preparation method of conductive basalt fiber material |
| CN114107963A (en) * | 2021-10-26 | 2022-03-01 | 重庆智笃新材料科技有限公司 | Basalt fiber continuous chemical plating device and application method |
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Application publication date: 20150603 |