CN1096826A - Method for showering metallizing on non-metallic material - Google Patents

Method for showering metallizing on non-metallic material Download PDF

Info

Publication number
CN1096826A
CN1096826A CN 93107514 CN93107514A CN1096826A CN 1096826 A CN1096826 A CN 1096826A CN 93107514 CN93107514 CN 93107514 CN 93107514 A CN93107514 A CN 93107514A CN 1096826 A CN1096826 A CN 1096826A
Authority
CN
China
Prior art keywords
plating
grams per
per liter
plating piece
sensitizing solution
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.)
Pending
Application number
CN 93107514
Other languages
Chinese (zh)
Inventor
刘振魁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN 93107514 priority Critical patent/CN1096826A/en
Publication of CN1096826A publication Critical patent/CN1096826A/en
Pending legal-status Critical Current

Links

Landscapes

  • Chemically Coating (AREA)

Abstract

The invention provides a kind of on non-metallic material the method for showering metallizing, it comprises, processing steps such as mechanical roughening treatment, sensitization processing, activation treatment, chemical shower plating.This method not only equipment and technology is simple, and can save starting material and chemical plating time.In addition, the present invention also provides and has formed simply acid sensitizing solution that concentration is low and alkaline sensitizing solution.

Description

Method for showering metallizing on non-metallic material
The present invention relates to method in the non-metal material surface electroless plating, relate in particular to method at non-metal material surface showering metallizings such as glass, glass reinforced plastic, resin, plastics, pottery, potter's clay, cement, building stones, timber, bamboo woods, this method is applicable to the various non-metallic process fine arts of processing goods, to replace the copper workmanship.
In the prior art, open day on March 30th, 1988 of Chinese patent CN87100440() disclose a kind of on electrically nonconducting material the method for metal brush-plating, this method is to carry out that mechanical roughening treatment, chemical roughen are handled, the solvent roughening treatment with non-conductive plating piece material is at first selective; Acid resistance, water-absorbent and polarity are strong and weak selects different sensitizing solutions to carry out sensitization to handle according to the plating piece material then; Activation treatment is at last with containing plating metal solion brush plating plating piece repeatedly, the metal of deposition desired thickness on the surface.Though this method has been broken away from the processing step of dipping in the bath, also have following shortcoming: (1) roughening treatment complexity needs to select multiple coarsing processing method according to the material difference; (2) complexity is handled in sensitization, according to the material character difference, need with multiple sensitization treatment solution, and the sensitizing solution moiety is many, the concentration height; (3) before carrying out chemical brush plating, also to reduce processing to plating piece, therefore increased the complicacy of technology; (4) brush plating is carried out with certain speed of relative movement with brushing plating pen at normal temperatures, and it is insufficient that plating bath reacts on the plating piece surface, and consumption plating bath amount is big, and the brush plating time is long, especially shows more outstanding to complex structure and the big plating piece of size.
The purpose of this invention is to provide a kind of sensitization treatment solution that composition is simple, concentration is low that on non-metallic material, uses in chemical method for showering metallizing and this method.
Provided by the invention on non-metallic material the method for showering metallizing realize by following processing step:
(1) mechanical roughening treatment
The present invention only uses mechanical alligatoring to plating piece, without chemical roughen and solvent alligatoring.The purpose of alligatoring is to make the surface of plating piece become rough surface on the microcosmic, to strengthen the bonding force of coating and plating piece.
The method of machinery alligatoring is to utilize sandblast machine under the 4-8 normal atmosphere 60-100 purpose silicon carbide or white fused alumina to be injected in the plating piece surface, makes the plating piece surface all be wetting ability.
Certainly, mechanical alligatoring also can be selected mill for use, methods such as emery cloth polishing.
(2) character of discriminating plating piece material
Differentiate whether the plating piece material is acidproof, so that use different sensitizing solutions.The more material of carbonate containing composition is not acidproof generally speaking, as marble, cement etc.; And pottery, potter's clay, glass, plastics, glass reinforced plastic etc. are acidproof.
Whether acidproof for the plating piece material, simple discrimination method is to drip acid sensitizing solution at the plating piece material surface, and drop has the bubble generation, and then this material is not acidproof, otherwise then acidproof.
(3) sensitization is handled
Whether acidproof according to the plating piece material, select different sensitizing solutions for use, acidproof plating piece need be used acid sensitizing solution; Not acidproof plating piece then uses alkaline sensitizing solution.
The sensitization treatment process be with through the plating piece surface temperature control after the mechanical roughening treatment in 22 ℃ of-33 ℃ of scopes, with acid sensitizing solution or alkaline sensitizing solution shower, make the plating piece surface evenly be covered with sensitizing solution, the plating piece that sensitization was handled dries or dries then.
(4) activation treatment
The purpose of activation treatment is to make the plating piece surface evenly be covered with the metal particle with catalytic activity, for the shower plating is prepared.
Activation treatment solution composition commonly used is:
AgNO 3The 5-15 grams per liter
NH 3H 2O 10-20 milliliter/liter
All the other water
Activating treatment process be with the plating piece surface temperature control after handling through sensitization in 22 ℃ of-33 ℃ of scopes, use the activation solution shower, at this moment chemical reaction takes place in plating piece surface:
The plating piece surface overstrike that this moment is white or light.
(5) chemical showering metallizing
After the activated processing of plating piece, with the plating piece surface temperature control in 22 ℃ of-33 ℃ of scopes, the plating bath that will contain following compositions is then heated to 50 ℃, by mixing with the reductive agent formalin than 1: 1, to plating piece shower repeatedly, chemical reaction is in time finished on the plating piece surface, and the cupric ion in the plating bath is constantly deposited on the plating piece surface, form the copper layer of combining closely, till required thickness of coating with plating piece.
Plating bath is formed and is divided into:
Plating bath:
CuSO 45H 2O 40-80 grams per liter
C 4H 4O 6KNa4H 2O 120-230 grams per liter
Na 2CO 3The 40-80 grams per liter
EDTA2Na 15-24 grams per liter
NaOH 50-90 grams per liter
All the other water
Reductive agent:
HCOH 80-120 milliliter/liter
All the other water
Need to prove that quality of coating is relevant with chemical reaction velocity with the plating bath consumption when forming coating, speed is fast, and the coating binding ability is poor; Speed is slow, and consumption plating bath amount is big; And chemical reaction velocity is relevant with the plating piece surface temperature, and temperature is low, and chemical reaction velocity is slow; The temperature height, chemical reaction velocity is fast.Showering metallizing of the present invention plating in 22 ℃ of-33 ℃ of scopes of temperature, it all is optimal that this temperature makes the plating bath amount of coating binding ability and consumption.
In above-mentioned processing step, sensitization is handled, and the shower method that activation treatment and electroless plating are used is with two containers, a liquid (sensitizing solution or activation solution or plating bath) of containing some amount, another is put plating piece, on the plating piece surface, liquid flows into the container of putting plating piece by the plating piece surface with the liquid shower, and it is complete to treat that liquid all drenches, plating piece is moved in the empty receptacle, again with the liquid shower on plating piece, according to the purpose of different process step, decision shower number of times.
Other metal of plating is to plate layer of copper, other metal of electricity consumption brush plating method plating then earlier by above-mentioned processing step on non-metallic material.
Sensitized solution provided by the invention has two kinds, and a kind of is the acid sensitizing solution that uses on the acid resistance plating piece; Another kind is the alkaline sensitizing solution that uses on acid resistance material not.All contained the metal ion of sensibilized during two kinds of sensitizing solutions are formed, this metal ion species is difficult for oxidation by air, is easy to be activated the metal ion oxidation in the liquid, and the most frequently used metal ion is a divalent tin ion.Two kinds of sensitizing solutions consist of:
Acid sensitizing solution
SnCl 22H 2O 6-24 grams per liter
36%-38% hydrochloric acid 10-34 grams per liter
All the other water
The alkalescence sensitizing solution
SnCl 22H 2O 6-49 grams per liter
NaOH 10-99 grams per liter
All the other water
Above-mentioned sensitizing solution compound method is simple, does not contain Toxic matter, environmentally safe.
Advantage of the present invention is that (1) all non-metallic material are only used mechanical roughening treatment, need not use chemical roughen and solvent alligatoring, has reduced process complexity; (2) the sensitization treatment solution is reduced to two kinds by multiple, for use provides convenience; (3) the sensitizing solution moiety is few, and concentration is low, and preparation is simple; (4) showering metallizing neither uses coating bath to soak, and does not also use brush to smear or the atomizer spray, only just can finish chemical plating metal purpose on non-metallic material with the plating bath shower on the plating piece surface with two containers, so equipment and technology are simple, easy to operate; (5) showering metallizing is to carry out on the certain temperature condition, not increasing under the equipment prerequisite, can improve electroless plating reaction speed, saves shower plating time and starting material; (6) showering metallizing is not limited by plating piece contour structures and size; (7) chemical reagent that uses in the showering metallizing is general reagent, does not contain Toxic matter, so environmentally safe, (8) also can adopt the brush coating technology after finishing showering metallizing, at its other metal or alloy of surperficial brush plating.
Describe the present invention in detail below by embodiment.
The embodiment I
The composition of acid sensitizing solution and preparation
No. 1 acid sensitizing solution
Form
SnCl 22H 2O 24 grams per liters
Hydrochloric acid 34 grams per liters of 36%-38%
All the other water
Compound method: (1) takes by weighing SnCl 22H 2O 24 grams place 1000 ml beakers, inject 800 ml tap water stirring and dissolving, and it is muddy that solution is.(2) take by weighing 34 hydrochloric acid that restrain 36%-38% and place 500 ml beakers, hydrochloric acid is injected above-mentioned 1000 ml beakers gradually, solution under agitation is clearly, stops to inject hydrochloric acid when being clearly.
(3) in solution, add on tap water to the 1000 milliliter scale, the acid sensitizing solution for preparing is kept in the Brown Glass Brown glass bottles and jars only.
No. 2 acid sensitizing solutions
Form
SnCl 22H 2O 10 grams per liters
Hydrochloric acid 18 grams per liters of 36%-38%
All the other water
Compound method is the same.
Embodiment 2
Alkalescence sensitizing solution composition and preparation
No. 1 alkaline sensitizing solution
Form
SnCl 22H 2O 18 grams per liters
NaOH 26 grams per liters
All the other water
Compound method: (1) takes by weighing 18 gram SnCl 22H 2O places 1000 ml beakers, injects 500 milliliters in tap water, stirring and dissolving.
(2) take by weighing 26 gram NaOH and place 1000 ml beakers, inject 400 ml tap water stirring and dissolving.
(3) two beaker solution are blended in one 1000 ml beaker, stir, and dash to 1000 milliliters of scales, alkaline sensitizing solution is kept in the Brown Glass Brown glass bottles and jars only with tap water.
No. 2 alkaline sensitizing solutions
Form
SnCl 22H 2O 10 grams per liters
NaOH 15 grams per liters
All the other water
Compound method is the same.
Embodiment 3
Activation solution is formed and preparation
Form
AgNO 315 grams per liters
NH 3H 220 milliliters/liter of O
All the other water
Compound method: (1) takes by weighing 15 gram AgNO 3Place 1000 ml beakers, inject 800 ml tap water stirring and dissolving, solution is muddy shape.
(2) measure 20 milliliters of NH 3H 2O places 500 ml beakers, with NH 3H 2O slowly pours in above-mentioned 1000 ml beakers and stirs till solution all is clearly.
(3) be diluted to 1000 milliliters with tap water.
Embodiment 4
In ceramic surface shower copper facing, the implementing process step is as follows:
(1) mechanical roughening treatment
Select 70 order silicon carbide for use, under the 4-8 normal atmosphere, sweep ceramic surface with the sandblast machine spray, till the unglazed bright spot in surface.
Remove surperficial dust with high-pressure air.
(2) sensitization is handled
Because of pottery is acidproof, use acid sensitizing solution.
Control through the ceramic surface temperature after the mechanical roughening treatment in 22 ℃ of-33 ℃ of scopes, with two plastic containers, No. 1 acid sensitizing solution containing some amount, another is put plating piece, with the sensitizing solution shower on plating piece, it is complete to treat that sensitizing solution all drenches, and plating piece is moved in the empty receptacle, again the sensitizing solution position be not stained with in the sensitizing solution shower.Shower so repeatedly, sensitizing solution evenly is covered with till.
(3) dry or dry plating piece.
(4) with the tap water above-mentioned plating piece that dries or dry of shower gently, attention can not make sensitizing solution wash out.
(5) activation treatment
Control the ceramic surface temperature in 22 ℃ of-33 ℃ of scopes, the activation solution shower for preparing with embodiment 3 then, the surperficial overstrike that this moment is white notes wanting even shower not have leak source.
(6) chemical shower copper facing
Select CuSO for use 45H 2O 40-80 grams per liter
C 4H 4O 6KNa4H 2O 120-230 grams per liter
Na 2CO 3The 40-80 grams per liter
EDTA2Na 15-24 grams per liter
NaOH 50-90 grams per liter
1000 milliliters in tap water
Obtain solution is a first liquid
Select HCOH 80-120 grams per liter for use
Tap water<1000 milliliter
Obtain solution is a second liquid
First liquid is heated to 50 ℃, by volume first liquid: second liquid=1: 1 mixed.
Will be in 22 ℃ of-33 ℃ of scopes through the ceramic plating piece surface temperature control after the activation treatment, with two vinyl discs, one fills above-mentioned mixed solution, another is placed ceramic plating piece, in plating piece surface shower, this moment, the plating piece surface formed the layer of copper layer, and mixed solution is shower repeatedly, the copper layer is thickeied gradually, till desired thickness.
(7) wash with tap water
Embodiment 5
Bamboo clappers shower copper facing, the implementing process step is as follows:
(1) mechanical roughening treatment
Select 60-80 order white fused alumina for use, carry out alligatoring with sandblast machine under the 4-8 normal atmosphere, the requirement of roughening treatment is with embodiment 4.
(2) sensitization is handled
Drip one with acid sensitizing solution and drop on the bamboo clappers, no bubble produces, so available acid sensitizing solution is handled.
Handle with No. 2 acid sensitizing solutions, treatment process is with embodiment 4.
All the other processing steps are with embodiment 4, and the result obtains copper-plated bamboo clappers.
Embodiment 6
Marble surface shower copper facing, the implementing process step is as follows:
(1) mechanical roughening treatment
Marble surface is polished with silicon carbide paper, with tap water flushing surface, washes down towards dried, dries or dries.
(2) sensitization is handled
The marble carbonate containing is so need to use alkaline sensitizing solution
Handle with No. 1 alkaline sensitizing solution, treatment process is with embodiment 4.
All the other processing steps are with embodiment 4, and the result obtains copper-plated marble.
Embodiment 7
Copper facing on cement plate, the implementing process step is as follows:
(1) mechanical roughening treatment
Select 80-100 purpose white fused alumina for use, carry out roughening treatment with sandblast machine under the 4-8 normal atmosphere, roughening treatment requires with embodiment 4.
(2) sensitization is handled
Drop on the cement plate with acid sensitizing solution, have bubble to produce, so use alkaline sensitizing solution.
Handle with No. 2 alkaline sensitizing solutions, treatment process is with embodiment 4.
All the other processing steps are with embodiment 4, and the result obtains copper-plated cement plate.
Embodiment 8
Ceramic surface is zinc-plated, and the implementing process step is as follows:
(1) presses the method for embodiment 4, in ceramic surface copper facing;
(2) water flushing;
(3) brush is zinc-plated
Select zinc sulfate 287 grams per liters for use
Ammoniacal liquor 300-340 milliliter/liter
All the other water
Compound method: take by weighing 287 gram zinc sulfate in 1000 ml beakers, inject 500 ml waters, 320 milliliters of ammoniacal liquor are poured into while stirring contained in the vitriolic beaker, stir, add water to 1000 milliliters;
The electricity consumption brush plating method is plated in the zinc plating bath on the pottery, and the result obtains galvanized pottery.
Embodiment 9
Marble surface is zinc-plated, and the implementing process step is as follows:
(1) presses the method for embodiment 6, in marble surface copper facing
(2) water flushing;
(3) brush is zinc-plated
Select tin protochloride 135 grams per liters for use
Tartrate 180 grams per liters
Quadrol 100-120 milliliter
All the other water
Compound method: take by weighing tin protochloride 135 grams, tartrate 180 grams place 1000 ml beakers, and inject 500 ml water stirring and dissolving, and 110 milliliters of quadrols not stopping slowly to inject beaker under the stirring, after stirring, are diluted with water to 1000 milliliters;
The electricity consumption brush plating method is plated in the tin plating bath on the marble, and the result obtains tinned marble.
Embodiment 10
Nickel plating on bamboo clappers, the implementing process step is as follows:
(1) presses the method for embodiment 5, copper facing on bamboo clappers;
(2) water flushing;
(3) brush nickel plating
Select single nickel salt 135.4 grams per liters for use
Ammonium citrate 62.1 grams per liters
Ammonium sulfate 10 grams per liters
60 milliliters/liter of ammoniacal liquor
All the other water
Compound method: take by weighing 135.4 gram single nickel salts, 62.1 gram ammonium citrates, 10 gram ammonium sulfate are inserted in 1000 ml beakers, and are injected 800 ml waters, and stirring and dissolving is injected 60 milliliters of ammoniacal liquor and is stirred, and injects water to 1000 milliliter.
The electricity consumption brush plating method is plated in nickel plating bath on the bamboo clappers, and the result obtains the bamboo clappers of nickel plating.

Claims (2)

1, a kind of on non-metallic material the method for showering metallizing, comprise roughening treatment, sensitization processing, activation treatment, no electrochemistry plating technic step, it is characterized in that following five steps;
(1) plating piece is carried out mechanical roughening treatment,
(2) differentiate whether acid resistance of plating piece material,
(3) sensitization is handled, will be in 22 ℃ of-33 ℃ of scopes through the plating piece surface temperature control of mechanical roughening treatment, acid sensitizing solution or alkaline sensitizing solution shower with containing following compositions make the plating piece surface evenly be covered with sensitizing solution, the plating piece that sensitization was handled dries or dries then
Acid sensitizing solution:
SnCl 22H 2O 6-24 grams per liter
The hydrochloric acid 15-34 grams per liter of 36%--38%
All the other water
The alkalescence sensitizing solution:
SnCl 22H 2O 6-49 grams per liter
NaOH 10-99 grams per liter
All the other water
(4) activation treatment, the plating piece surface temperature control after will handling through sensitization with the activation solution shower that contains following compositions, makes the plating piece surface evenly be covered with Ag in 22 ℃ of-33 ℃ of scopes then,
AgNO 3The 5-15 grams per liter
NH 3H 2O 10-20 milliliter/liter
All the other water
(5) chemical shower plating, will be in 22 ℃ of-33 ℃ of scopes through the plating piece surface temperature control after the activation treatment, the plating bath that will contain following compositions is then heated to 50 ℃, mixed with the reductive agent formalin, plating piece is carried out shower repeatedly in 1: 1 by volume, up to required thickness of coating
Plating bath:
CuSO 45H 2O 40-80 grams per liter
C 4H 4O 6KNa4H 2O 120-230 grams per liter
Na 2CO 3The 40-80 grams per liter
EDTA2Na 15-24 grams per liter
NaOH 50-90 grams per liter
All the other water
Reductive agent:
HCOH 80-120 milliliter/liter
All the other water
2, method according to claim 1 is behind the plating piece copper coating at other metal of plating on the non-metallic material, uses the electro-plating method plating again.
CN 93107514 1993-06-25 1993-06-25 Method for showering metallizing on non-metallic material Pending CN1096826A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 93107514 CN1096826A (en) 1993-06-25 1993-06-25 Method for showering metallizing on non-metallic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 93107514 CN1096826A (en) 1993-06-25 1993-06-25 Method for showering metallizing on non-metallic material

Publications (1)

Publication Number Publication Date
CN1096826A true CN1096826A (en) 1994-12-28

Family

ID=4986730

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 93107514 Pending CN1096826A (en) 1993-06-25 1993-06-25 Method for showering metallizing on non-metallic material

Country Status (1)

Country Link
CN (1) CN1096826A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309862C (en) * 2001-07-02 2007-04-11 希普雷公司 Nonelectrolytic gold plating liquid and method thereof
CN103436869A (en) * 2013-08-13 2013-12-11 中国地质大学(武汉) Method for plating nanogold plating on inner wall of glass container
CN107225329A (en) * 2017-07-10 2017-10-03 北京工业大学 A kind of method for improving glass copper facing bonding strength
CN107955940A (en) * 2017-12-04 2018-04-24 上海安费诺永亿通讯电子有限公司 It is a kind of that the gold-plated technique of topochemistry is carried out on moulding surface
CN111663124A (en) * 2020-06-11 2020-09-15 大连理工大学 Method for plating silver on silicon carbide surface
CN112979344A (en) * 2021-03-16 2021-06-18 河海大学 Antibacterial protective layer prepared on concrete surface based on chemical plating method and preparation method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1309862C (en) * 2001-07-02 2007-04-11 希普雷公司 Nonelectrolytic gold plating liquid and method thereof
CN103436869A (en) * 2013-08-13 2013-12-11 中国地质大学(武汉) Method for plating nanogold plating on inner wall of glass container
CN103436869B (en) * 2013-08-13 2016-03-09 中国地质大学(武汉) A kind of method obtaining nanometer gold coating at Glass Containers inwall
CN107225329A (en) * 2017-07-10 2017-10-03 北京工业大学 A kind of method for improving glass copper facing bonding strength
CN107955940A (en) * 2017-12-04 2018-04-24 上海安费诺永亿通讯电子有限公司 It is a kind of that the gold-plated technique of topochemistry is carried out on moulding surface
CN111663124A (en) * 2020-06-11 2020-09-15 大连理工大学 Method for plating silver on silicon carbide surface
CN112979344A (en) * 2021-03-16 2021-06-18 河海大学 Antibacterial protective layer prepared on concrete surface based on chemical plating method and preparation method

Similar Documents

Publication Publication Date Title
CN87100440A (en) The method of metal brush-plating on electrically nonconducting material
CN1223702C (en) Plating method of metal film on surface of polymer
CN1280452C (en) Copper plating bath and method for plating substrate by using the same
CN1084396C (en) Silver plating bath and silver plating method using same
CN101033550A (en) Micro-corrosion liquid and application thereof in printing wiring board silver aggradation pretreatment
CN1275636A (en) Electroplating method and the used liquid front body
CN1016365B (en) Improved reducing agent and method for electroless deposition of silver
CN1270020C (en) Electromagnetic shield textiles and its preparing method
CN86102615A (en) Assembling die
CN1497070A (en) Noncyanide electrolytic solution for gold plating
CN1096826A (en) Method for showering metallizing on non-metallic material
CN1190522C (en) Electrolytic solution for electrochemical deposit of palladium or its alloys
CN88100692A (en) The metallic substance of zinc-base composite plating and electrochemical plating
CN1745194A (en) Method of forming a conductive metal region on a substrate
CN1502720A (en) Methyl free copper plating method and used solution thereof
CN1156625C (en) Chemical Silver plating method for organic fibre
CN1033709C (en) Process for roll plating of non-metallic surface
CN1300877A (en) Local electroplating method for substrate
CN1205626C (en) High corrosion-resistant R-Fe-B-base bonded magnet and method of manufacturing the same
CN1304679C (en) Copper-in-tin electromagnetic screen textile and method for preparing same
CN1249267C (en) Plated resin molding products and manufacturing method thereof
CN1214990C (en) Palladium complex salt and use thereof for adjusting palladium concentration of electrolytic solution for deposit of palladium or its alloys
CN1441087A (en) Nickel electric plating liquid
CN1066690A (en) High-temperature corrosion resistant coating and preparation process thereof
CN1495287A (en) Plating method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication