text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 16, 1997
|Filing date
|Mar 11, 1992
|Priority date
|Mar 11, 1992
|Fee status
|Publication number
|George S. Bokisa
|Original Assignee
|Mcgean-Rohco, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (13), Referenced by (23), Classifications (16), Legal Events (8)
|External Links: USPTO, USPTO Assignment, Espacenet
Cn H2n+1 CH(OH)--(CH2)m --SO3 H (II)
This invention relates to the electrodeposition of tin, lead, and tin-lead alloys, and particularly to a plating bath which contains at least one soluble bismuth salt of an alkane sulfonic acid or alkanol sulfonic acid and which deposits smooth and level tin, lead and/or tin-lead alloy coatings.
Aqueous acidic plating baths for depositing tin and/or lead coatings on substrates have been known in the art, and most of these baths contain, in addition to the water-soluble tin and/or lead salts, fluoborates, fluosilicates, sulfates, sulfamates, etc. Plating baths containing fluoborate have been used widely to permit high-speed, uniform metal plating of tin, lead or tin-lead alloys. However, baths containing fluoborates generally are quite corrosive and toxic, requiring special equipment which is expensive and presents difficulties in operation, including the disposal of waste water.
An aqueous acidic bath for electroplating tin-bismuth alloy upon a metal object such as a frame of a computer including fluoboric acid, tin fluoborate and a bismuth oxide-bismuth sulfate mixture is described in U.S. Pat. No. 3,663,384. The concentration of bismuth ions is from 0.01 to 0.05 grams per liter.
U.S. Pat. No. 4,331,518 describes electroplating baths containing tin ions and a chelate salt comprising an acid bismuth sulfate gluconate. The bath produces a tin-lead alloy which is resistant to the effects of tin pests and the formation of tin whiskers.
U.S. Pat. No. 4,565,609 describes a bath for the electrodeposition of tin, lead, and tin-lead alloys which comprises a lead and/or tin alkyl sulfonate, an alkyl sulfonic acid in sufficient amount to impart a Ph of below about 3 to the bath, and various additives to improve the brightness of the deposits and other properties. The various additives include quaternary nitrogen wetting agents, alkylene oxides, pyridine compounds, aromatic aldehydes, acid aldehyde and/or a bismuth compound. The bismuth compounds are used in the bath to improve the low current density brightness of the deposits. Bismuth nitrate is an example of an acceptable bismuth compound. U.S. Pat. Nos. 4,565,610 and 4,599,149 also describe similar tin, lead and tin-lead containing baths which contain lead and/or tin alkyl sulfonate, alkyl sulfonic acids and, optionally, bismuth compounds such as bismuth nitrate.
U.S. Pat. No. 5,039,576 describes a bath and method for electrodepositing a tin-bismuth alloy onto a conductive substrate. The bath comprises tin and bismuth ion in aqueous solution, and an alkyl sulfonic or polysulfonic acid or salt as the electrolyte. The sulfonic acid component is present in an amount sufficient to maintain the bismuth in solution. The alloy which is deposited contains greater than 10% bismuth, and in a preferred embodiment, the alloy is the eutectic mixture of tin and bismuth. In particular, the baths contain alkyl sulfonic or polysulfonic acids or their salts. Thus, baths may comprise stannous methane sulfonate, bismuth methane sulfonate and methane sulfonic acid.
U.S. Pat. No. 4,617,097 also describes electroplating baths for tin, lead and tin-lead alloys which contain a lead and/or tin alkyl or alkyloyl sulfonate, an excess of an alkyl or alkyloyl sulfonic acid sufficient to bring the Ph of the bath below about 3, and various additives that are reported to improve the brightness of the deposits, the useful current density ranges, and/or the solderability of tin-lead alloy deposits. Such additives include certain alkylene oxide compounds, quaternary nitrogen wetting agents containing a fatty acid radical, aromatic aldehydes, acetaldehydes and/or bismuth compounds. Bismuth nitrate is an example of a bismuth salt which can be included in the baths.
It now has been found that a smooth and level deposit of tin, lead or tin-lead alloy can be deposited on a substrate from an aqueous plating bath which comprises (A) at least one bath-soluble metal salt selected from the group consisting of a stannous salt, a lead salt, or a mixture of stannous and lead salts, (B) an acid selected from the group consisting of sulfuric or fluoboric acid; and (C) an effective amount of at least one soluble bismuth salt of an alkane sulfonic acid or an alkanol sulfonic acid. Optionally, the aqueous plating bath may further comprise (D) at least one surfactant.
The plating baths of the present invention comprise tin ions, lead ions, or a mixture of tin and lead ions, an acid from the group consisting of sulfuric or fluoboric acid, an effective amount of at least one soluble bismuth salt of an alkane sulfonic acid or alkanol sulfonic acid, and, optionally and preferably, at least one surfactant. The optional surfactant may be any suitable amphoteric, nonionic, cationic or anionic surfactant and, preferably, is a cationic or anionic surfactant.
The plating baths of the present invention contain water-soluble stannous salts, water-soluble lead salts, or mixtures thereof, depending on the metal or metals to be deposited by the bath on the substrate. Obviously, when a tin deposit is desired, the lead ion is omitted from the bath, and, conversely, when a lead deposit is desired, the stannous ion is omitted from the bath. Generally, the anion of the metal salt corresponds to the anion of the acid used in the bath. For example, when sulfuric acid is used in the plating bath, the salts may be stannous sulfate or lead sulfate, and when the acid is fluoboric acid, the salts are generally stannous fluoborate and lead fluoborate.
The amount of metal ion or ions in the bath may vary over a wide range depending upon the desired properties of the plating to be deposited on a substrate. Generally, from about 5 to about 350 grams per liter or more of the metal ion or ions will be included in the plating baths of the invention. The amount of sulfuric or fluoboric acid included in the baths also may vary over a wide range such as from 50 to about 500 grams per liter. Generally, the aqueous acidic plating baths of the invention are maintained at a pH of less than about 3.
The bismuth salts of alkane sulfonic acids (C) are derived from alkane sulfonic acids represented by the following Formula I:
wherein R is an alkyl group containing from about 1 to about 12 carbon atoms and more preferably, from about 1 to 6 carbon atoms. Examples of such alkane sulfonic acids include, for example, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, 2-propane sulfonic acid, butane sulfonic acid, 2-butane sulfonic acid, pentane sulfonic acid, hexane sulfonic acid, decane sulfonic acid and dodecane sulfonic acid. Bismuth salts of the individual alkane sulfonic acids or mixtures of any of the above alkane sulfonic acids can be utilized in the plating baths of the invention.
The bismuth salts of alkanol sulfonic acids (C) are derived from alkanol sulfonic acids represented by the following Formula II: ##STR1## wherein n is from 0 to about 10, m is from 1 to about 11 and the sum of m+n is from 1 up to about 1. As can be seen from the above Formula II, the hydroxy group may be a terminal or internal hydroxy group. Examples of useful alkanol sulfonic acids include 2-hydroxy ethyl-1-sulfonic acid, 1-hydroxy propyl-2-sulfonic acid, 2-hydroxy propyl-1-sulfonic acid, 3-hydroxy-propyl-1-sulfonic acid, 2-hydroxy butyl-1-sulfonic acid, 4-hydroxy butyl-1-sulfonic acid, 2-hydroxy-pentyl-1-sulfonic acid, 4-hydroxy-pentyl-1-sulfonic acid, 2-hydroxy-hexyl-1-sulfonic acid, 2-hydroxy decyl-1-sulfonic acid, 2-hydroxy dodecyl-1-sulfonic acid.
The alkane sulfonic acids and alkanol sulfonic acids are available commercially and can also be prepared by a variety of methods known in the art. One method comprises the catalytic oxidation of mercaptans or aliphatic sulfides having the formula R1 Sn R2 wherein R1 or R2 are alkyl groups and n is a positive integer between 1 and 6. Air or oxygen may be used as the oxidizing agent, and various nitrogen oxides can be employed as catalysts. The oxidation generally is effected at temperatures below about 150� C. Such oxidation processes are described and claimed in U.S. Pat. Nos. 2,433,395 and 2,433,396. Alternatively, chlorine can be used as the oxidizing agent. Bismuth salts of such acids are prepared, for example, by dissolving bismuth trioxide in a hot concentrated aqueous solution of an alkane or alkanol sulfonic acid.
The concentration of the soluble bismuth salt of an alkane sulfonic acid or alkanol sulfonic acid (C) in the plating baths of the invention is generally an amount which provides less than about 10 grams of bismuth ions per liter of bath, and in one embodiment, less than about 2 g/l. In one preferred embodiment, the bath contains from about 0.05 to about 1.5 g/l of bismuth ions.
It is within the scope of the invention to optionally include in the plating bath: (D), one or more surfactants compatible with each of the bath soluble metal salts (A), the acids (B) and the soluble bismuth salts (C). In general, the plating baths of the present invention will optionally contain at least one surfactant in a concentration of from about 0.01 to about 50 grams per liter of bath and more preferably from about 0.05 to about 20 grams per liter of bath. As noted above, the surfactant (D) may be at least one surfactant including amphoteric, nonionic, cationic, or anionic surfactants; or mixtures thereof. More often, the surfactant (D) is at least one cationic or anionic surfactant; or mixtures thereof.
A variety of nonionic surfactants which can be utilized in the present invention are the condensation products of ethylene oxide and/or propylene oxide with compounds containing a hydroxy, mercapto or amino group containing at least one N--H. Examples of materials containing hydroxyl groups include alkyl phenols, styrenated phenols, fatty alcohols, fatty acids, polyalkylene glycols, etc. Examples of materials containing amino groups include alkylamines and polyamines, fatty acid amides, etc.
Examples of nonionic surfactants useful in the plating baths of the invention include ether containing surfactants having the Formula III:
R--O-- (CH2)n O!x H (III)
wherein R is an aryl or alkyl group containing from about 6 to 20 carbon atoms, n is two or three, and x is an integer between 2 and 100. Such surfactants are produced generally by treating fatty alcohols or alkyl or alkoxy substituted phenols or naphthols with excess ethylene oxide or propylene oxide. The alkyl carbon chain may contain from about 14 to 24 carbon atoms and may be derived from a long chain fatty alcohol such as oleyl alcohol or stearyl alcohol.
Nonionic polyoxyethylene compounds of this type are described in U.S. Pat. No. 3,855,085. Such polyoxyethylene compounds are available commercially under the general trade designations "Surfynol" by Air Products and Chemicals, Inc. of Wayne, Pa., and under the designation "Pluronic" or "Tetronic" by BASF Wyandotte Corp. of Wyandotte, Mich. Examples of specific polyoxyethylene condensation products useful in the invention include "Surfynol 465" which is a product obtained by reacting about 10 moles of ethylene oxide with 1 mole of tetramethyldecynediol. "Surfynol 485" is the product obtained by reacting 30 moles of ethylene oxide with tetramethyldecynediol. "Pluronic L 35" is a product obtained by reacting 22 moles of ethylene oxide with polypropylene glycol obtained by the condensation of 16 moles of propylene oxide.
Alkoxylated amine, long chain fatty amine, long chain fatty acid, alkanol amines, diamines, amides, alkanol amides and polyglycol-type surfactants known in the art are also useful. One type of amine surfactant found particularly useful in a tin or lead plating bath is the group obtained by the addition of a mixture of propylene oxide and ethylene oxide to diamines. More specifically, compounds formed by the addition of propylene oxide to ethylene diamine followed by the addition of ethylene oxide are useful and are available commercially from BASF Wyandotte, Ind. Chemical Group under the general trade designation "Tetronic".
Carbowax-type surfactants which are polyethylene glycols having different molecular weights also are useful. For example Carbowax No. 1000 has a molecular weight range of from about 950 to 1050 and contains from 20 to 24 ethoxy units per molecule. Carbowax No. 4000 has a molecular weight range of from about 3000 to 3700 and contains from 68 to 85 ethoxy units per molecule. Other known nonionic glycol derivatives such as polyalkylene glycol ethers and methoxy polyethylene glycols which are available commercially can be utilized as surfactants in the compositions of the invention.
Ethylene oxide condensation products with fatty acids also are useful non-ionic surfactants. Many of these are available commercially such as under the general tradename "Ethofat" from Armak Ind. Examples include condensate of coco acids, oleic acid, etc. Ethylene oxide condensates of fatty acid amides, e.g. oleamide, also are available from Armak Ind.
In some of the baths, improved results are obtained when polyoxyalkylated glycols, phenols and/or naphthols are included. For example ethylene oxide and propylene oxide condensates with aliphatic alcohols, sorbitan alkyl esters, alkyl, alkoxy and styrenated phenols and naphthols are useful additives. About 6 to about 40 moles of the oxide may be condensed with the above identified compound. Many of these condensates are available commercially under such trade names as "Tween" from ICI America, "Triton" from Rohm & Haas Co., "Tergitol" from Union Carbide, and "Igepal" from General Aniline and Film Corp.
The surfactants (D) utilized in the plating baths of the present invention also may be amphoteric surfactants. The preferred amphoteric surfactants include betaines and sulfobetatnes, and sulfated or sulfonated adducts of the condensation products of ethylene oxide and/or propylene oxide with an alkyl amine or diamine. The betaines may be represented by the general Formula IV: ##STR2## wherein R1 is an alkyl group containing from about 8 to 20 carbon atoms, and R2 and R3 are alkyl groups containing from 1 to about 4 carbon atoms.
Typical betaines include lauryldimethylammonium betaine and stearyl dimethylammonium betaine. Sulfated and sulfonated adducts include Triton QS-15 (Rohm & Haas Co.), a sulfated adduct of an ethoxylated alkylamine, Miranol HS, a sodium salt of a sulfonated lauric derivative, Miranol OS, a sodium salt of a sulfonated oleic acid, etc.
Cationic surfactants also are useful in the plating baths of the present invention and such surfactants may be selected from the group consisting of higher alkyl amine salts, quaternary ammonium salts, alkyl pyridinium salts and alkyl imidazolium salts.
Cationic surfactants obtained by condensation of various amounts of ethylene oxide or propylene oxide with primary fatty amines are useful and may be represented by the following Formula V: ##STR3## wherein R is a fatty acid alkyl group containing from about 8 to about 22 carbon atoms, R1 is an alkylene radical containing up to about 5 carbon atoms, R2 and R3 are each independently an ethylene or propylene group, a is 0 or 1, and x, y and z are each independently integers from 1 to about 30, and the sum of x, y, and z is an integer of from about 2 to about 50.
More particularly, the alkoxylated amines utilized in the baths of the invention are represented by the Formulae VI and VII: ##STR4## wherein R4 is a fatty acid alkyl group containing from 12 to 18 carbon atoms, and x, y and z are as defined in Formula V.
The above described cationic surfactants are known in the art and are available from a variety of commercial sources. The surfactants of the type represented by Formula VI can be prepared by condensing various amounts of ethylene oxide with primary fatty amines which may be a single amine or a mixture of amines such as are obtained by the hydrolysis of tallow oils, sperm oils, coconut oils, etc. Specific examples of fatty acid amines containing from 8 to 22 carbon atoms include saturated as well as unsaturated aliphatic amines such as octyl amine, decyl amine, lauryl amine, stearyl amine, oleyl amine, myristyl amine, palmityl amine, dodecyl amine, and octadecyl amine.
The alkoxylated amines which are useful in the plating baths of the invention can be prepared as mentioned above, by condensing alkylene oxides with the above-described primary amines by techniques known to those in the art. A number of such alkoxylated amines is commercially available from a variety of sources.
The above described amines can be prepared, as mentioned above, by condensing alkylene oxides with the above-described primary amines by techniques known to those in the art. A number of such alkoxylated amines is commercially available from a variety of sources. The alkoxylated amines of the type represented by Formula VI are available from the Armak Chemical Division of Akzona, Inc., Chicago, Ill., under the general trade designation "Ethomeen". Specific examples of such products include "Ethomeen C/15" which is an ethylene oxide condensate of a coconut fatty amine containing about 5 moles of ethylene oxide; "Ethomeen C/20" and "C/25" which also are ethylene oxide condensation products from coconut fatty amine containing about 10 and 15 moles of ethylene oxide respectively; "Ethomeen S/15" and "S/20" which are ethylene oxide condensation products with stearyl amine containing about 5 and 10 moles of ethylene oxide per mole of amine respectively; and "Ethomeen T/15" and "T/25" which are ethylene oxide condensation products of tallow amine containing about 5 and 15 moles of ethylene oxide per mole of amine respectively. Commercially available examples of the alkoxylated amines of the type represented by formula (5) include "Ethoduomeen I/13" and "T/20" which are ethylene oxide condensation products of N-tallow trimethylene diamine containing about 3 and 10 moles of ethylene oxide per mole of diamine respectively.
Another type of useful cationic surfactant is represented by the Formula VIII: ##STR5## where R is an alkyl group containing from about 8 to about 12 carbon atoms, Y is a methyl or a hydroxyl group, m and n are integers, the sum of which is from about 2 to about 20.
The amine ethoxylate surfactants of the type represented by Formula VIII exhibit the characteristics of both cationic and nonionic surfactants with the nonionic properties increasing at the higher levels of ethoxylation. That is, as the sum of x and y increases, the ethoxylated amine behaves more like a nonionic surfactant.
The surfactants represented by Formula VIII wherein Y is a methyl group are available commercially such as from Texaco Chemical Company under the trade designation "M-300 Series". The M-300 Series compounds currently available from Texaco and which have been found to be useful in the aqueous acid plating baths of the invention include those designated as M-302, M-305, M-310, M-315 and M-320 which contain a total to 2, 5, 10, 15 and 20 moles of ethylene oxide respectively. In all of these compounds, R is a mixture of 10 and 12 carbon alkyl groups.
The cationic surfactant also may be:
(a) a quaternary ammonium salt of the Formula IX: ##STR6## wherein X represents a halogen, a hydroxyl group, or the residue of a C1-5 alkanesulfonic acid; R1 represents alkyl group R' and R" represent a C1-4 alkyl group; and R'" represents a C1-10 alkyl group or a benzyl group;
(b) pyridinium salts represented by the general Formula X: ##STR7## wherein X represents a halogen, a hydroxyl group, or the residue of a C1-5 alkanesulfonic acid; R1 represents a C8-20 alkyl group; and Ra represents hydrogen or a C1-4 alkyl group;
(c) imidazolinium salts represented by the general Formula XI: ##STR8## wherein X represents a halogen, a hydroxyl group, or the residue of a C1-10 alkanesulfonic acid; R1 represents a C8-20 alkyl group; Rd represents a hydroxy-containing C1-5 alkyl group; and R'" represents a C1-10 alkyl group or a benzyl group; and
(d) higher alkyl amine salts represented by the general Formula XII:
R1--NH3 !.sup.(+) CH3 --(CH2)n --COO.sup.(-)(XII)
wherein R1 represents a C8-20 alkyl group; and n is from about 0 to about 4.
Examples of the above described cationic surfactants, in the form of salts, are lauryltrimethylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, lauryldimethylethylammonium salt, octadecyldimethylethylammonlum salt, dimethylbenzyllaurylammonium salt, cetyldimethylbenzylammonium salt, octadecyldimethylbenzylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt, hexadecylpyridinium salt, laurylpyridinium salt, dodecylpicolinium salt, 1-hydroxyethyl-1-benzyl-2-laurylimidazoliniumsalt, 1-hydroxyethyl-1-benzyl-2-oleylimidazoliniumsalt, stearylamine acetate, laurylamine acetate, and octadecylamine acetate.
The surfactants also may be anionic surfactants. Examples of useful anionic surfactants include sulfated alkyl alcohols, sulfated lower ethoxylated alkyl alcohols, and their salts such as alkali metal salts. Examples of such surfactants include sodium lauryl sulfate (Duponol C or QC from DuPont), sodium mixed long chain alcohol sulfates available from DuPont under the designation Duponol WN, sodium octyl sulfate available from Alcolac, Ltd. under the designation Sipex OLS, Sodium tridecyl ether sulfate (Sipex EST), sodium lauryl ether sulfate (Sipon ES), magnesium lauryl sulfate (Sipon LM), the ammonium salt of lauryl sulfate (Sipon L-22), diethanolamino lauryl sulfate (Sipon LD), sodium dodecylbenzene sulfonate (Siponate DS), etc.
Antioxidants normally used in tin, lead and tin/lead baths may be included in the baths of this invention. For example catechol (1,2-dihydroxybenzene) is useful as an antioxidant stabilizer in the baths and prevents air oxidation of stannous to stannic tin. Generally amounts of from about 0.05 to about 2 grams of antioxidant per liter of bath is sufficient.
The acid, tin, lead, and tin-lead plating baths of the present invention which contain at least one soluble bismuth salt of an alkane sulfonic acid or alkanol sulfonic acid, deposit a smooth and level coating of the metal or alloy on substrates at any conventional temperature used or normally used with tin and/or lead plating baths, and over a wide current density range such as from 1 to 2000 amperes per square foot (ASF).
The following examples (except for the control example) illustrate the plating baths of the invention. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, temperatures are in degrees Celsius, and pressure is at or near atmospheric pressure.
The utility of the plating baths of the present invention in depositing metal coatings is demonstrated by conducting plating tests in standard 267 ml Hull cells using tin as the anode. Steel (or brass) panels are plated at a current of 1 amp for a period of three (3) minutes. Mild mechanical bath agitation is employed, and the bath temperature is maintained at about 20� to about 25� C. The results of the plating tests are shown below.
An aqueous plating bath is prepared by mixing with water, sufficient quantities of stannous sulfate to provide 15 g/l of stannous ion, 10% by volume of sulfuric acid, 0.4 cc of a 100 gram per liter solution of the bismuth salt of methane sulfonic acid (0.16 g/l as bismuth metal), 2% by weight of an aqueous mixture containing 35 grams per liter of Ethomeen T/20 and 2.5 grams per liter of catechol, and 2% by weight of a solution of 75 ml. of Dupanol SP (an anionic sodium alcohol sulfate) per liter of water. The bismuth salt used in this example is prepared by dissolving 111 grams of bismuth trioxide in 1 liter of hot 40% by volume, 70% methane sulfonic acid.
Plating is effected with this bath in a hull cell at room temperature. A complete end-to-end panel coverage is achieved.
A steel panel is plated with the plating bath of Example 1 except that the bath does not contain the bismuth salt. The bath produces a satin finish from the HCD to 2 ASF. The plate then fades to a skip plate at 1 ASF and is void approaching zero.
The bath is prepared similar to the bath of Example 1 except the bath contains only 0.08 g/l of bismuth. Essentially the same results are obtained as in Example 1 when a panel is electroplated with this bath.
An aqueous acidic bath is prepared by mixing water with sufficient quantities of stannous fluoborate to provide the bath with about 15 g/l of stannous ion, 200 g/l of fluoboric acid, 2% by weight of an aqueous solution containing 35 grams per liter of Ethomeen T/20 and 2.5 grams per liter of catechol, and 2% of an aqueous solution containing 75 ml. of Dupanol SP per liter. A plating test is conducted with this bath, and the resulting panel exhibits a large low current density improvement.
An aqueous bath is prepared containing 15 g/l of stannous tin, 10% sulfuric acid, 1 cc of the bismuth salt of methane sulfonic acid, 2% by weight of an aqueous mixture containing 35 g/l of Ethomeen T/20 and 2.5 grams per liter of catechol, and 2% by weight of an aqueous solution containing 75 ml. per liter of Dupanol SP. Brass panels and steel panels are plated at 20 ASF for 12 minutes with this bath. The deposits on the panels and the appearance of matte acid tin.
In order to demonstrate quantitatively the increase in LD covering power obtained by the plating baths of the present invention, steel panels are plated at 1 ampere for 3 minutes using the plating baths of Examples 1 and 2 of the invention and the bath of Control Example 1. The panels are subjected to X-ray fluorescence analysis, and the thicknesses are reported in microinches for a given current density. The results of this test are summarized in the following table.
TABLE______________________________________ ASF 6 4 2 0.5______________________________________Control Example 1 63 50 36 15Standard Acid TinExample 1 62 40 39 34Containing 0.16 g/l BiExample 2 65 41 46 36Containing 0.08 g/l Bi______________________________________
As can be seen from the above results, the inclusion of a small amount of bismuth significantly improves the low current density covering power.
In practice, the improved tin, lead, and tin-lead alloy plating baths containing the compositions of the invention may be operated on a continuous or intermittent basis, and from time to time, components of the bath have to be replenished. The various components may be added singularly as required or may be added in combination. The amounts of the various additive compositions to be added to the plating baths may be varied over a wide range depending on the nature and performance of the plating bath to which the composition is added. Such amounts can be determined readily by one skilled in the art.
The electroplating baths of the present invention exhibit a significant increase in the throwing power in the low current density (LCD) range. Use of the baths containing the bismuth ions also results in some grain refining.
One of the advantages of the plating baths of the present invention, particularly the tin containing at least one soluble bismuth salt of an alkane sulfonic acid is that the baths reduce whiskering. Whiskering is undesirable because of the aesthetic problems created, and further because of its corrosive nature when present in plating baths. The plating baths of the present invention which do not contain fluoride or fluoborate ions are less corrosive to machinery and glass parts, and also permit the use of titanium and titanium alloy anode baskets. It also has been observed that anode dissolution is improved in the plating baths of the present invention which results in less anode polarization and a reduced amount of stannate tin in the bath.
The coatings deposited from the plating baths of the invention are useful in electronic circuits, electronic devices and electrical connectors. The surface layers of tin, lead and tin-lead alloys can be used as protective layers to prevent corrosion or in a patterning procedure during the fabrication of printed circuits or integrated circuits. The coatings also provide chemically stable surfaces for soldering on printed wire boards, etc.
While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.
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|Aug 17, 2000
|Dr.-Ing. Max Schl�tter Gmbh & Co. Kg
|Solution of electrolytes and method for producing lead-tin layers
|Jan 4, 2008
|Aug 21, 2008
|Arkema Inc.
|High speed tin plating process
|U.S. Classification
|205/254, 106/1.25, 205/253, 205/299, 205/302
|International Classification
|Cooperative Classification
|European Classification
|Mar 11, 1992
Owner name: MCGEAN-ROHCO, INC., OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BOKISA, GEORGE S.;REEL/FRAME:006052/0713
Effective date: 19920307
|Mar 16, 2001
Owner name: ATOTECH DEUTSCHLAND GMBH, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MCGEAN-ROHCO, INC.;REEL/FRAME:011641/0912
Effective date: 20010131
|Jul 10, 2001
|Maintenance fee reminder mailed
|Nov 19, 2001
|Surcharge for late payment
|Nov 19, 2001
|Fee payment
Year of fee payment: 4
|Jul 6, 2005
|Maintenance fee reminder mailed
|Dec 16, 2005
|Lapse for failure to pay maintenance fees
|Feb 14, 2006
|Expired due to failure to pay maintenance fee
Effective date: 20051216


text:
Flowers on Argyle has been providing wonderful flowers to the people of the Southern Highlands for over 31 years! Cindy and her talented team will create the perfect wedding, birthday, condolence or celebration flowers for every occasion. We also have a great range of teddies, balloons, plants, chocolates and gourmet baskets... Please call us today for personal, prompt and great value service!
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subset: commoncrawl


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List all words ending with muras
Only the word muras was found, nothing longer.
Some random words: do igloo oeillade epexegeses gharial aoudad sris
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Anatomy Lessons: How to improve faster in 6 steps!'Life Drawing 5' by algaegoblinDo you know how to sketch human figures but do you want to refine your anatomy skills? Or do you not know anatomy at all and you are tired to trust your imagination? Did you notice you create disproportions in your drawings?If you are aspiring artists and you already have your own style, you might as well believe you have no need of a guide, but you are wrong. Before exaggerating human proportions and begin to have your own style, you first have to know the basics. This little guide is the result of an accurate research and 5 years of high school of art, and it's created for all those who want to learn something new or just make a useful review.For those who have already studied art, my suggestion is to go to step 6 or trying to repeat all steps in Digital format. STEP 1First of all, if you want to learn faster you should draw using traditional tools.
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Strider Cheats for Playstation 4Home / Playstation 4 /
This page contains Cheats for Strider organized by sections for Playstation 4. This game has "Action Adventure" as genre, made by Double Helix Games, released on Feb 18, 2014. If you can't find a hint or secret in our list, then please check this page periodically for the latest updates.
- Developer: Double Helix Games
- Publisher: Capcom
- Genre: Action Adventure
- Release: Feb 18, 2014
- ESRB: Everyone 10+
To unlock the following Trophies, complete the following tasks:..From: Miley1921
To unlock the following Secret Trophies, complete the following tasks:..From: spectator
Video Walkthroughs
If you know cheats, secrets, hints, glitches or other level guides for this game that can help others leveling up, then please Submit your Cheats and share your insights and experience with other gamers.
Stuck in this game? Set a specific, clearly defined question and let other gamers answer your question or view answers to previously asked questions. If you think you are an expert then please try to help others with their questions.
I'm missing just one energy upgrade. I've been at each location at least 10 times. I seriously stayed up for 18 hours searching for one item. I'm on hard, so that means the next time I okay the game I...
Posted on: 02-24-2014
Strider - New York Comic Con Trailer 2013
- Oct 13, 2013, Views: 116
Strider - Let's Play Trailer
- Feb 24, 2014, Views: 103
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What does TESE stand for?
TESE stands for Thesaurus Europeo dei Sistemi Educativi
This definition appears very rarely and is found in the following Acronym Finder categories:
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See other definitions of TESE
Other Resources:
We have 12 other meanings of TESE in our Acronym Attic
- Abbreviation Database Surfer
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- Transposable Element Simulator Dynamics (genomics simulation)
- Tredyffrin Easttown School District (Pennsylvania)
- Technical Education and Skills Development Act of 1994 (Philippines)
- Technical Education and Skills Development Authority (Philippines)
- Technical Education and Skills Development Project (Philippines)
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Cooking & Recipes Articles
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Sometimes it's planned, other times it's spontaneous. However it happens, eating together has been... read more
My parents retired to the family room and left the five of us girls to talk, laugh, drink post... read more
I began my Garden-Fresh Cookbook blog with a delicious seafood dish, Skillet Sea Scallops, so when... read more
I grabbed my mom's old camera bag that has been turned into a vintage-looking purse, and headed... read more
Planning parties and other large gatherings can be stressful. To make it easier, here is a... read more
With the spinach fettuccine taking only 3 minutes to cook al dente and the scallions sautéed with... read more
The worst spring season the Northwest has seen in years isn't showing in the growth of the seeds I... read more
Have you ever left a restaurant feeling a little ill and were concerned it might be more than just... read more
It's hard to say no to your kids when they want to help you bake, but now you don't have to. Try... read more
When preparing party recipes for Christmas, keep the menu simple. With a little organization and a... read more
Chicken salads are always a staple for any picnic or outside gathering. Next time you're in need of... read more
Preparing to have family and friends over for a nice Christmas party? Here are 15 Christmas party... read more
Enjoy these picnic food recipes to help you prepare for the perfect picnic! Picnics are a great... read more
I have grown up in a family in which the only meat eaten in the house was chicken, turkey, or... read more
These basic sugar cookie recipes offer a delicious treat for any gathering of family or friends... read more
I knew I was going to love the Cucumbers With Feta Cheese Dressing from The Garden Fresh Cookbook... read more
Any dish with avocados in the title, and I'm sold. In need of comfort food after a long week, I... read more
This is a must-try from The Garden-Fresh Cookbook—a must! I couldn't help myself from sneaking a... read more
I knew this blog post would come, yes readers: I had my first disaster in the kitchen. While... read more
The house phone rang as I was peeling a banana for my Mint Mango Smoothie; my sister was calling... read more
Springtime means time for farmers' markets! Cities are bursting with small and large street markets... read more
Good morning, readers! I woke up bright and early with a to-do list about a foot long— time to... read more
After weeks of rainy weather and a hint of sunshine in the Pacific Northwest, I began to see life... read more
Sliced apples and cheddar cheese used to be my go-to snack while spending late evenings on campus.... read more
I think I got my love for spicy food from my dad: I would watch him shake the hot sauce or spoon... read more
While tending to my separate vegetable, potato, and herb gardens (the last, grown in a bag) keeps... read more
Ever wake up feeling like treating yourself to something special? This morning, after a run in the... read more
As I wrote about in my last post, I've been preparing for a new garden! With the weeds pulled and... read more
Sometimes it's hard to pick just one dish from The Garden-Fresh Cookbook! To solve this dilemma, I... read more
I spent this past week in Minnesota with family and friends, mourning the passing of my grandfather... read more
Since I have been on a recent potato kick, with a small patch freshly planted in my garden, I... read more
My herbs in a bag, which I talked about planting in a previous post, are now placed in a... read more
I eat a lot of fish, usually steamed (salmon) or baked (flounder, cod, or scrod). So the... read more


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Natural beauty tips, the best makeup, cosmetics and beauty products, and more
Patricia Senft, owner of The Ten Spot Beauty Bar in Yaletown. shares everything you need to know about nail care for this summer
Tired of the same old Swedish massage? Maybe it's time to try something different at the spa
Keep your lips looking spring-ready with these fabulous liquid lipsticks


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Ted Cruz offered an "apology" to New Yorkers offended by his criticism of "New York values," but used the apology to slam "liberal politicians" in office.00:45
based on a latin american tradition, a special day has been created where people can eliminate negativity from their lives. good riddance day gave new yorkers the chance to write down whatever it was they'd like to eject from their lives and then put in the bin. in times square on sunday, queues of people wanted to 'shred it and forget it'.01:30
admit it - deep down, we're all swifties.04:07
thousands of mike brown protestors gathered in times square tonight. large group of michael brown protestors have gathered in new york city. thousands of peo...02:03
just stretch your imagination for a moment - li hongbo's surprising sculptures go to show that in the world of art, what you see is not always what you get.01:22
in new york city, the greatest pizza restaurant is debated daily. how come? it is easy - new yorkers love pizza.02:20
ilex consumer products group, a baltimore based company which owns and manages health and beauty as well as over the counter otc drug brands, launched digel, a new antacid antigas brand, just in time for all the overindulging and stress of the holidays. the new digestive aid, which is being promoted with integrated tv and digital advertising, grassroots and public relations, launched with the brand tagline when you overdo, undo.01:26
two days after superstorm sandy brought new york to a standstill, residents itching to get back to work walked over the brooklyn bridge wednesday morning. su...00:45
her kadını dize getirecek bir erkek vardır.00:46
new yorker commercial.00:55
new yorker - reklam filmi03:39
new yorker imagefilm 201100:46
new yorker dergisinin komik reklam filmi.00:30
new yorker bikini commercial.01:40
bailout frenzy in new york's times square as company hands out cash. the bailout booth will travel soon to washington, dc , boston, and philadelphia.01:21
100 new yorkers lock lips to set a chain kissing world record.00:51
düğün gecesi bu ateşe kim dayanabilir ki...01:30
obama karikatürüdünya çapında küçük çapta bir olay yarattı...01:30
new yorker'ın obama karikatürü obama yandaşlarını kızdırdı.02:48
prodigy - dirty new yorker [new]02:48
prodigy - dirty new yorker music video00:49
new yorker - dress for the moment - bus stop00:51
çok yaratıcı ve komik bir reklam!00:51
tv commercial by new yorker. winter 2006.


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Customer Reviews
There are no reviews for this product yet. Please share your thoughts on this product!
Sending the same ornament to different places? If you order more than one of an item and want them shipped to different addresses, please order them individually. We will ask you for the individual shipping addresses later in the ordering process.
Angel Playing Violin Christmas Ornament
Personalized Christmas Ornament
The precision of the cutting of this lovely wood angel ornament made in Germany is done on both sides, so no matter which way this sweet cherub hangs on your tree, she will be displayed in all her glory. This German ornament shows a young angel playing her violin, perhaps in a celestial orchestra, making the sweetest Christmas carol music. The first violins had strings were plucked rather than played with a bow as they are now. This angel ornament makes an ideal addition to a violin or fiddle player's tree.
Material: German Wood
Ornaments shown on our site are personalized, as examples only, so you can see where we put the words/names you give us. Some ornaments allow you to select hair or uniform color. If there is no color choice, it is not available on that particular ornament. We will do everything possible to catch any mistakes in spelling, etc., but are not responsible if we do as you request, and it is then not correct. The ornament you see above is the way it will look when you get it, except for the personalizing instructions you give us and any optional attributes you select.
Read what our customers say about our Personalized Christmas Ornaments and their shopping experience!Hover over testimonials to stop scrolling
12/13/2015 - "Very pleased with the quick turn around with my personalized order! Anonymous Respondent"
12/11/2015 - "This is my second purchase for this holiday season. I look forward to seeing these gifts! Allison S."
12/2/2015 - "Loved my ornaments. I have already ordered more and I have recommended ornament shop to several friends! Brian D."
12/15/2015 - "Like the choices available, would have liked more ethnic choices to choose from. I was late ordering my ornaments this year, not happy with myself, but it is what it is. Will just have to order earlier next year. Ordered in the past couple of years, Merry Christmas to everyone at Ornament Shop!! Joline G."
3/3/2016 - "OrnamentShop is my FAVORITE place to purchase Christmas ornaments from. I've been shopping from the online site for several years now and I LOVE EVERYTHING I've ever purchased and HIGHLY recommend them to anyone who may be looking for ornaments!!!!!!!!!!Robyn M."
12/27/2015 - "We bought the Christmas tree with 25 name plates and had 19 names put on it for my mother in law. My in laws have 19 grand kids and 2 on the way and when my mother in law opened it she was amazed as was everyone of the craftsmanship. I will be ordering more and can't say enough good things about Ornament Shop. Thank you all you are the best. Renee .M."
8/31/2015 - "Love the selection of ornaments. I was able to buy my family yearly ornaments all in one place. Renee Y."
11/20/2015 - "This is I think the 3rd or 4th year I've ordered from you and always happy with the selection, the promptness and the product itself... see you next year : )Stephanie W. "
1/27/2016 - "Great service! Conadine S."
12/14/2015 - "Had been looking for a train ornament for awhile and this one with 5 names fit the bill. Couldn't find it anywhere else on-line or at craft fairs. Margo W."


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Panama Papers – What you need to know |Infographic by CourersTrack
Source: CouriersTrack
The U.S.'s Computer Emergency Response Team (CERT) issued a warning to critical infrastructure firms on Wednesday about a serious security …Read More
The source code to the infamous Zeus crimeware kit, which has been sold on underground forums for years, has been …Read More
Hackers have attacked around 40 South Korean government and private websites. Targets include websites at the presidential office, the foreign …Read More
A recent security report has highlighted a significant rise in the number of malware and malvertising attacks on social networks. …Read More
March 14th, Adobe confirmed that there is an un-patched bug in Adobe Flash Player using Microsoft Excel documents. Hackers are …Read More
The London Stock Exchange website was attacked by malware hidden inside an advert on February 28th. The Stock Exchange also …Read More
Microsoft's Malware Protection Engine has been patched as Argeniss security expert identifies an 'elevation of privilege' vulnerability in which an …Read More
RSA Security is one of the biggest players in the enterprise security landscape, featuring advanced authentication, access control and data …Read More


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First Look at DC Rebirth Designs For Bizarro, Red Robin, Batman Beyond & More
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Augie goes back a decade to Marvel's experiment with "Eden's Trail," a sideways comic from Steve Uy and Chuck Austen presented in the Marvelscope format. Plus, Uy's stronger follow-up series, "Feather."
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...I prefer to tutor in library or public places. I really enjoy tutoring students and make them understand various concepts in math and science. When I see my students improve on their knowledge and grades, it makes me feel that I have been successful in teaching them.I have been tutoring Algebra 1 since last five years.
Buford, GAView Tutor
...While attending Duke, I tutored elementary school students in reading and math skills with a Durham tutoring center, helping under-performing students successfully catch up to their peers. Now that I have moved to Atlanta to work as an attorney, I hope to continue tutoring students. My teaching is driven by a great love of learning and helping students.
Atlanta, GAView Tutor
I received my bachelor's degree (cum laude) in 2005 and my master's degree in 2010. Presently, I am finishing up my doctorate in communication at Georgia State University. Although I have only limited experience teaching, I love knowledge and learning, and I am thrilled to pass this on to others.
Atlanta, GAView Tutor
...Math can be a hard subject area for students to excel in because of the complicated methods that several school systems are implementing within their lesson plans. I am an efficient and simple math teacher who is confident in making sure that each student understands the basic fundamentals in order to tackle more complex and layered math problems. Problem solving is a major key!
Lawrenceville, GAView Tutor
...Currently, I'm the Director of the Quality Management group at a Fortune 300 company. As part of my duties, I have taught introductory descriptive and inferential statistics to students learning process improvement techniques for over 8 years. And I also am a certified tutor for Huntington Learning Center and have over 2 years experience tutoring students in SAT math, geometry and algebra.
Dacula, GAView Tutor


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Conchita Wurst's Eurovision Win Marred by Anti-Gay Comments
Conchita Wurst's recent victory at Eurovision drew controversy as expected. The anti-gay lobby of Russia branded the so-called Austrian bearded woman's win at the song contest as "the end of Europe."
A debate involving politicians and celebrities was broadcast on Russian TV networks after the 2014 competition was wrapped up in Copenhagen. The outspoken Russian politician Vladimir Zhirinovsky said, "There is no limit to our outrage. It has turned wild. There are no more men or women in Europe, just it."
Meanwhile, Deputy Prime Minister of Russia Dmitry Rogozin tweeted that the result "showed supporters of European integration their European future - a bearded girl." Moscow Correspondent Steve Rosenberg confirmed during an appearance on BBC that Russia didn't take it "well at all."
Russia, Belarus and Ukraine petitioners had demanded that Wurst be dropped from the competition, calling her act "ridiculous." However, the 25-year-old drag artist was a favorite to win all along. Things got heated up when the Russian entry The Tolmachevy Sisters was booed whenever they received points.
However, Wurst whose real name is Tom Neuwirth remained in good spirit after the win. "We are unstoppable," she said at a press conference after the finale. "I really dream of a world where we don't have to talk about unnecessary things like sexuality, where you're from or who you love. This is not what it's all about. I really felt like tonight, Europe showed that we are a unity full of respect and tolerance."
She also told reporters in Vienna, "That was obviously meant for certain politicians whom we all know." Asked if it was directed at Russian president Vladimir Putin, who passed an anti-gay law last year, Wurst said, "among others."
- Chris Brown Sued for Allegedly Stealing a Fan's Hat at Concert
- Listen to Previews of Justin Bieber's Remix of Drake's 'One Dance'
- Take a Look at Ciara's Exotic Vacation in Mexico With Russell Wilson and Son Future
- Dwayne 'The Rock' Johnson's Daughter Impressed With His Tattoo
- Artist of the Week: Fifth Harmony
- Johnny Depp Is 'Blackmailed' by 'Manipulative' Amber Heard, Says Friend Doug Stanhope
- Kim Kardashian Shows Off Her Curves in Cleavage-Baring Dress During Lunch With Kanye West
- 'Game of Thrones' 6.07 Preview: More Unexpected Returns


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(402) 563-5158View Additional Phone Numbers1414 15th St, Columbus, NE 68601-5226http://www.ne-fcu.org
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Give us a call at 1-800-735-5387 or instant message one of our wood pellet specialists.
Other high-cost proposals include replacing a natural gas heating system at the modern New Hampshire Hospital with a wood pellet boiler and installing storm ... more
The wood pellet manufacturer will run largely on solar power and have a gas line available as a back-up source of energy. The location was chosen partly ... more
International Woodfuels announced Tuesday it plans to build a $20 million wood pellet manufacturing plant in the central Maine town of Burnham. ... more
The company behind a wood pellet mill planned for south-west Victoria, wants to proceed with the project, despite difficulty in securing a site. ... more
2011 All Rights Reserved. | WoodPellets.com, LLC is affiliated with American Biomass Distribution, LLC | Patents Pending


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Royksopp album stream
Wow, I remember So Easy from these guys when I was like 11 years old, great song.
These guys have a new one coming out? Nice, I'll definitely listen
Was expecting black metal when i saw this name
already saw on grooveshark. sweet album.
listened to a few and im intrigued.
Seems pretty generic and run of the mill. Would make for good background music though.
"Was expecting black metal when i saw this name"
bored the shit out of me to be honest.
enjoying this one really much, thank you.
so far what ive heard; its not bad.
• Michael Gira Accused of Rape• R.I.P. Lemmy• R.I.P. David Bowie• Scott Weiland dead at 48 • Rush drummer retires• The Story So Far's vocalist dropk..• Killswitch Engage debut new single• Deftones stream new single• Riverside guitarist dies• Phil Anselmo causes uproar over N..
• Russian Circles debut new song• Another new Thrice track• Volbeat Seals The Deal With Lyric..• R.I.P. Nick Menza• New Willow Smith, Michael Cera• Say Anything's new music video• New Alaskalana Reissue and EP• New Silent Planet single• Hangman Drop New Single• Joey Jordison's other new band• New Despised Icon Video• New P.O.S. single • R.I.P. John Berry• The Fall of Troy release OK#2• Gojira post second single» see all news
Bands: A B C D E F G H I J K L M N O P Q R S T U V W X Y Z


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Houses to let in Short Beck, Feltwell, Thetford IP26 - 5 bedrooms
Keywords and filters like garden and parking live here
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£2,300 pcm (£531 pw)
South Street, Hockwold, Thetford IP26Detached house to rent - 5 bedrooms
Situated in a non estate position within the popular village of Hockwold is this spacious detached family home. The accommodation comprises: Entrance hall, cloakroom, lounge, dining room, kitchen, utility room, study/office, master bedroom with en ...
Note: Distances are straight line measurements
- Lakenheath (1.1 miles)
- Brandon (3.5 miles)


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At right: The Many Adventures of Horace Horsecollar the D'oh attraction as seen from the top of Monte Carlo
Join D'oh and your other woodland friends in a rocking honey-bee ride vehicle for a trip to the 100 Element Wood. You'll help D'oh lose all his earthly possessions to a natural disaster, meet neffalumps and joozles, and celebrate Kronk's bris!
Please don't try Pirate Mode
© copyright 2011–2016
A Pants Aflame production


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Yes, sure, check magazines and you will find at least 10 new exercise programs. Or perhaps a friend told you about a great training technique that you might want to try out.
But what are the movements that you should cover in any exercise program?
There are 6 movement patterns that you should concentrate on in any exercise program to prevent wear and tear, allow variety and work out all the muscle groups without creating imbalance that might lead to pain and injuries.
Movement patterns that you not want to miss:
Squat exercises - Do anything that lowers your hips and toward the floor.
Bend exercises - Movements that bend from the upper torso to the floor.
Lunge exercises - Place one foot in front and one foot behind you while you bring the knee 3 inches to the floor. This can be executed in many different directions.
Pull exercises - As the name implies any pulling motion towards your body.
Push exercises - And any exercise that pushes items away from you.
Twist exercises - It can be as simple as rotating your upper torso from one side to the next.
All those movements need to be incorporated into any exercise program. And if not, add them on. Hence, if you just run, it will not be enough. The same thing for just walking. Oh wait, is your favorite exercises crunches or chest presses? You miss out on many exercises that you can do even without the gym.
Stay focused.
Sign up for your FREE weightloss solutions at www.stefanaschan.com