TWI421382B - Semi-bright nickel plating bath and method of using same - Google Patents
Semi-bright nickel plating bath and method of using same Download PDFInfo
- Publication number
- TWI421382B TWI421382B TW099135543A TW99135543A TWI421382B TW I421382 B TWI421382 B TW I421382B TW 099135543 A TW099135543 A TW 099135543A TW 99135543 A TW99135543 A TW 99135543A TW I421382 B TWI421382 B TW I421382B
- Authority
- TW
- Taiwan
- Prior art keywords
- nickel
- bath
- liter
- deposit
- electroplating bath
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
Description
本發明大致關於一種半光亮鎳電鍍浴，其提供關於調平、延展性與應力之良好性質，及其為實質上無硫。The present invention is generally directed to a semi-bright nickel electroplating bath that provides good properties with respect to leveling, ductility and stress, and which is substantially sulfur free.
光亮鎳電鍍浴係用於汽車、電氣、器材、五金及其他工業。光亮鎳電鍍之最重要功能為作為電鍍鉻用底塗層，幫助修整機達成平滑光亮之修整，及提供大量之腐蝕保護。Bright nickel plating baths are used in the automotive, electrical, equipment, hardware and other industries. The most important function of bright nickel plating is as an undercoat for chrome plating, which helps the finisher achieve smooth and smooth finishing and provides a lot of corrosion protection.
對於需要高程度之基本金屬腐蝕保護的裝飾性電鍍部分，光亮鎳沉積物幾乎始終結合後續之光亮鎳與鉻沉積物使用。半光亮鎳沉積物一般為沉積在該部分上之全部鎳的約60及70%，其以最小之總鎳厚度與最佳之外觀提供最高之基本金屬腐蝕保護程度。For decorative plating parts that require a high degree of base metal corrosion protection, bright nickel deposits are almost always used in conjunction with subsequent bright nickel and chromium deposits. The semi-bright nickel deposit is typically about 60 and 70% of the total nickel deposited on the portion, providing the highest degree of base metal corrosion protection with a minimum total nickel thickness and an optimum appearance.
最常用之鎳電鍍浴為已知為瓦茲(Watts)浴之硫酸鹽浴。典型瓦茲浴含有約20-40盎司/加侖(02/gal)之硫酸鎳、3-12盎司/加侖之氯化鎳、與4-6盎司/加侖之硼酸，且在約2.0-5.2之pH範圍、90-160℉之溫度範圍與約10-60 ASF範圍之電流密度操作。大量硫酸鎳提供必要之鎳離子濃度，氯化鎳改良陽極腐蝕且增加導電性，及硼酸係作為維持pH之弱緩衝液。另外，為了達成鎳電鍍沉積物之光亮及有光澤外觀，其經常將有機與無機試劑(亮光劑)加入電解質。所添加亮光劑之型式及其濃度決定鎳沉積物之外觀，即明亮、光亮、半光亮、緞紋等。The most commonly used nickel plating bath is a sulfate bath known as a Watts bath. A typical watts bath contains about 20-40 ounces per gallon (02/gal) of nickel sulfate, 3-12 ounces per gallon of nickel chloride, and 4-6 ounces per gallon of boric acid, and at a pH of about 2.0-5.2. The range, temperature range of 90-160 °F and current density operation in the range of about 10-60 ASF. A large amount of nickel sulfate provides the necessary nickel ion concentration, nickel chloride improves anode corrosion and increases conductivity, and boric acid acts as a weak buffer to maintain pH. In addition, in order to achieve a bright and shiny appearance of nickel electroplated deposits, organic and inorganic reagents (shiners) are often added to the electrolyte. The type of the added brightener and its concentration determine the appearance of the nickel deposit, namely bright, bright, semi-bright, satin, and the like.
傳統上已使用薰草素由瓦茲鎳浴獲得高調平、延展、半光亮及無硫鎳沉積物。然而現在已有無薰草素溶液。如名稱所暗示，半光亮鎳沉積物修整為半光澤，但是係特別地因其拋光與擦光之容易性而發展。在替代方案中，如果繼而電鍍光亮鎳則可排除擦光。亮度及平滑度係依操作條件而定。Highly leveled, extended, semi-bright and sulfur-free nickel deposits have traditionally been obtained from the Watts nickel bath using xanthan. However, there is now no humectin solution. As the name implies, semi-bright nickel deposits are trimmed to a semi-gloss, but are developed especially due to their ease of polishing and polishing. In the alternative, if the bright nickel is subsequently plated, the buffing can be excluded. Brightness and smoothness are determined by operating conditions.
半光亮鎳修整如此易於擦光及/或拋光的原因之一為沉積物之結構為柱狀，而光亮鎳修整之結構為板狀(片狀)。然而沈積物之結構可隨各種添加劑、pH變化、電流密度、或溶液攪拌增加而改變，其除非影響沉積物之性質(如內部應力)，否則不成問題。One of the reasons why the semi-bright nickel trimming is so easy to polish and/or polish is that the structure of the deposit is columnar, and the structure of the bright nickel trim is plate-like (sheet-like). However, the structure of the deposit can vary with various additives, pH changes, current densities, or increased agitation of the solution, which is not a problem unless it affects the properties of the deposit, such as internal stress.
電鍍鎳沉積物之內部應力可為壓縮性或拉伸性。壓縮性應力為沉積物擴張而釋放應力。相反地，拉伸性應力為沉積物收縮。高壓縮沉積物可造成起泡、捲曲，或者造成沉積物自基板分離，而具高拉伸應力之沉積物除了裂開及疲乏強度減小，亦會造成捲曲。The internal stress of the electroplated nickel deposit can be compressive or stretchable. The compressive stress releases the stress as the deposit expands. Conversely, tensile stress is the shrinkage of the deposit. Highly compressive deposits can cause blistering, curling, or separation of deposits from the substrate, while deposits with high tensile stress can cause curling in addition to cracking and reduced fatigue strength.
在鎳電鍍浴(特別是半光亮鎳法)中使用薰草素作為添加劑製造調平優良之延展性、有光澤沉積物為已知的。亦已知獲得之調平程度通常與電鍍浴中之薰草素濃度成正比。全薰草素浴一般含約150至約200毫克/公升之薰草素與約30毫克/公升之甲醛。如此可知浴中之高薰草素濃度產生最佳之調平。The use of xanthan as an additive in the nickel electroplating bath (especially the semi-bright nickel method) is known for the production of fine ductile, lustrous deposits. It is also known that the degree of leveling obtained is generally proportional to the concentration of xanthophyll in the electroplating bath. The full lavender bath typically contains from about 150 to about 200 mg/liter of oxacin and about 30 mg/liter of formaldehyde. This shows that the high concentration of oxacin in the bath produces the best leveling.
然而此特徵之壽命短，因為此高薰草素濃度亦造成有害瓦解或降解產物之高形成速率。此等降解產物因其會造成不易藉後續光亮鎳沉積物增亮之不均勻、無光澤灰暗區域，其會降低由電鍍浴中特定薰草素濃度獲得之調平，及其會降低鎳沉積物之有益物理性質而遭異議。However, this feature has a short life because this high kasugain concentration also causes a high rate of formation of harmful decomposition or degradation products. Such degradation products may cause uneven, dull, dark areas that are not readily brightened by subsequent bright nickel deposits, which may reduce the leveling obtained by the specific concentration of the xanthanes in the plating bath, and may reduce nickel deposits. It is objectionable because of its beneficial physical properties.
因為已知薰草素在許多條件下瓦解或降解，所以必須監測含薰草素電鍍浴之降解使得電鍍不受負面地影響。亦已建議為了減少降解產物及如此增加浴壽命而降低浴中之薰草素濃度，但是此薰草素濃度降低經常附帶調平損失，亦使浴對降解物累積更敏感。亦己建議使用各種添加劑(如甲醛與水合氯醛)以助於克服薰草素降解產物之不欲影響。然而使用此添加劑有相當之限制，因為均勻適度濃度之此等材料不僅增加鎳電鍍沉積物之抗拉應力，亦顯著地降低薰草素之調平作用。Since korbutin is known to disintegrate or degrade under many conditions, it is necessary to monitor the degradation of the bath containing the xanthanol plating so that the plating is not adversely affected. It has also been suggested to reduce the concentration of the kakudin in the bath in order to reduce the degradation products and thus increase the bath life, but this reduction in the concentration of the kakunin is often accompanied by a leveling loss, which also makes the bath more sensitive to the accumulation of degradants. Various additives such as formaldehyde and chloral hydrate have also been suggested to help overcome the undesired effects of the degradation products of xanthophylls. However, the use of this additive is rather limited, as uniform and moderate concentrations of such materials not only increase the tensile stress of the nickel electroplated deposit, but also significantly reduce the leveling effect of the xanthan.
亦已建議使用一種包含組合量之薰草素化合物與芳基羥基羧酸化合物的酸性鎳水性電鍍浴，例如Tremmel之美國專利第4,441,969號所述，其標的在此全部併入作為參考。It has also been proposed to use an aqueous nickel-based electroplating bath comprising a combined amount of a humectin compound and an aryl hydroxy carboxylic acid compound, as described in U.S. Patent No. 4,441,969, the entire disclosure of which is incorporated herein by reference.
因為所示薰草素系浴之缺點，研究者長期以來已嚐試發展一種可提供藉薰草素系浴(在電鍍業界被視為標準)達成之調平的半光亮鎳電鍍浴。調平指沉積物填入表面缺陷(如刮痕或拋光線)及使之平滑的能力。提供此等高調平沉積物但不犧牲沉積物延展性與應力亦為重要的。進一步較佳為鎳沉積物含小於0.004%之硫。Because of the shortcomings of the Kaempfera-based baths, researchers have long attempted to develop a semi-bright nickel electroplating bath that provides a leveling that can be achieved by a bath with a lavender bath (which is considered standard in the electroplating industry). Leveling refers to the ability of deposits to fill surface defects, such as scratches or polishing lines, and to smooth them. It is also important to provide such high leveling deposits without sacrificing deposit ductility and stress. It is further preferred that the nickel deposit contains less than 0.004% sulfur.
自1970年後期起，電鍍供應商已提議許多據稱調平如同薰草素浴之浴調配物。然而迄今此等浴調配物均無法符合必要之標準。據信迄今發展之最佳浴在相同沉積物厚度僅可達到薰草素系沉積物調平之約65%。Since the late 1970s, electroplating suppliers have proposed a number of bath formulations that are said to be leveled as a bath with a xanthan bath. However, to date these bath formulations have failed to meet the necessary standards. It is believed that the best bath developed to date can only achieve about 65% of the leveling of the Kaempferal sediments in the same sediment thickness.
如以上所解釋，雖然薰草素之調平卓越，但是薰草素瓦解且形成有害降解產物，及此等降解產物僅可將電鍍浴以分批碳處理移除。此等處理為昂貴及耗時且通常必須歷時至少一個月，在某些情形甚至數週而完成。因此在此技藝需要提供一種無薰草素而提供類似調平特徵之鎳電鍍浴。As explained above, although the leveling of the xanthan is excellent, the kaempferin disintegrates and forms harmful degradation products, and such degradation products can only remove the electroplating bath by batch carbon treatment. Such processing is expensive and time consuming and typically must take at least one month, in some cases even weeks. It is therefore desirable in the art to provide a nickel electroplating bath that provides no similar leveling characteristics without xanthophylls.
現有之半光亮鎳溶液使用己炔二醇與丁炔二醇組合醛(如水合氯醛、甲醛與向日醛)，進一步組合柳酸或苯甲酸。此等浴之內部應力相當高，範圍為約8,000 psi拉伸至約15,000 psi拉伸。另外，此等浴之調平均無近乎全薰草素系統之調平。The existing semi-bright nickel solution uses a combination of hexynediol and butynediol (such as chloral hydrate, formaldehyde and acetal) to further combine sulphuric acid or benzoic acid. The internal stress of these baths is quite high, ranging from about 8,000 psi to about 15,000 psi stretch. In addition, the average of these baths is not nearly equal to the level of the full-energy system.
因此希望提供一種無薰草素半光亮鎳電鍍浴，其接近薰草素浴之調平特徵，實際上無硫，及應力與延展性符合汽車要求。It is therefore desirable to provide a non-phumogen semi-bright nickel electroplating bath that is close to the leveling characteristics of the xanthan bath, which is virtually sulfur free, and that the stress and ductility are in accordance with automotive requirements.
本發明之一個目的為提供一種高調平半光亮鎳沉積物，其延展性優良且應力非常低。It is an object of the present invention to provide a high leveling semi-bright nickel deposit which is excellent in ductility and very low in stress.
本發明之另一個目的為提供一種無薰草素半光亮鎳電鍍浴，其接近薰草素浴之調平特徵且實際上無硫。Another object of the present invention is to provide a xanthanes-free semi-bright nickel electroplating bath that is close to the leveling characteristics of the xanthan bath and is virtually free of sulfur.
本發明之另一個目的為提供一種半光亮鎳電鍍浴，其不需要醛而提供可接受之同步厚度及電解電位(STEP)結果。Another object of the present invention is to provide a semi-bright nickel electroplating bath that provides acceptable simultaneous thickness and electrolysis potential (STEP) results without the need for aldehydes.
本發明之又另一個目的為提供一種半光亮鎳電鍍浴，其在浴壽命期間提供良好之安定性。Still another object of the present invention is to provide a semi-bright nickel electroplating bath that provides good stability during bath life.
關於此點，本發明大致關於一種用於對基板電鍍半光亮鎳沉積物之鎳電鍍浴，該鎳電鍍浴包含：In this regard, the present invention is generally directed to a nickel electroplating bath for electroplating a semi-bright nickel deposit to a substrate, the nickel electroplating bath comprising:
a) 鎳離子(如得自硫酸鎳與氯化鎳之混合物)；a) nickel ions (such as from a mixture of nickel sulfate and nickel chloride);
b) 經鹵化物取代乙酸、丙酸或以上之鹽；及b) substituting a halide for acetic acid, propionic acid or a salt thereof;
c) 選自由己炔二醇、丁炔二醇及以上之組合所組成的二醇中之至少一種。c) at least one selected from the group consisting of hexynediol, butynediol, and a combination of the above.
在另一個具體實例中，本發明大致關於一種電鍍基板而對其製造無硫半光亮鎳沉積物之方法，其包含以下之步驟：In another embodiment, the invention is generally directed to a method of making a sulfur-free semi-bright nickel deposit by electroplating a substrate comprising the steps of:
a) 提供一種鎳電鍍浴，其包含：a) providing a nickel plating bath comprising:
i) 鎳離子(如得自硫酸鎳與氯化鎳之混合物)；i) nickel ions (eg from a mixture of nickel sulfate and nickel chloride);
ii) 經鹵化物取代乙酸、丙酸或以上之鹽；及Ii) substituting a halide for acetic acid, propionic acid or a salt thereof;
iii) 選自由己炔二醇、丁炔二醇及以上之組合所組成的二醇中之至少一種；及Iii) at least one selected from the group consisting of hexynediol, butynediol, and a combination of the above; and
b) 使基板接觸鎳電鍍浴且施加電流，而對基板提供半光亮鎳沉積物。b) contacting the substrate with a nickel plating bath and applying a current to provide a semi-bright nickel deposit to the substrate.
本發明大致關於一種鎳電鍍浴，其包括經鹵化物取代乙酸、丙酸或以上之鹽組合己炔二醇及/或丁炔二醇。The present invention generally relates to a nickel electroplating bath comprising a halide-substituted acetic acid, propionic acid or a salt thereof in combination with hexynediol and/or butynediol.
更特定言之，本發明大致關於一種無薰草素鎳電鍍浴，其提供含薰草素鎳電鍍浴可達成之調平特徵。More particularly, the present invention is generally directed to a non-norrazine nickel electroplating bath that provides a leveling feature that can be achieved with a xanthanol electroplating bath.
在一個具體實例中，本發明大致關於一種鎳電鍍浴，其包含：In one embodiment, the invention is generally directed to a nickel electroplating bath comprising:
a) 鎳離子之來源；a) the source of nickel ions;
b) 經鹵化物取代乙酸、丙酸或以上之鹽；及b) substituting a halide for acetic acid, propionic acid or a salt thereof;
c) 選自己炔二醇、丁炔二醇及以上之組合的二醇中之至少一種。c) selecting at least one of an acetylene glycol, a butynediol, and a diol of the above combination.
如以上所討論，鎳電鍍浴通常含有硫酸鎳與氯化鎳。另外，一般加入硼酸以控制溶液之pH。As discussed above, nickel plating baths typically contain nickel sulfate and nickel chloride. In addition, boric acid is generally added to control the pH of the solution.
電鍍浴應含有經鹵化物取代乙酸、丙酸、或其鹽。其較佳為單氯乙酸，然而二氯乙酸或三氯乙酸亦適合。上述酸通常如鈉、鉀、鋰、鎂與鎳鹽而加入，因為添加酸趨於使浴之pH太低。可溶性鹽(如單氯乙酸鈉)之濃度較佳為約2.0至4.0克/公升之間，但是可為低至0.5克/公升至高達20克/公升之範圍。The electroplating bath should contain a halide-substituted acetic acid, propionic acid, or a salt thereof. It is preferably monochloroacetic acid, however dichloroacetic acid or trichloroacetic acid is also suitable. The above acids are usually added as sodium, potassium, lithium, magnesium and nickel salts because the addition of the acid tends to make the pH of the bath too low. The concentration of soluble salts (e.g., sodium monochloroacetate) is preferably between about 2.0 and 4.0 grams per liter, but can range from as low as 0.5 grams per liter to as high as 20 grams per liter.
己炔二醇濃度應為100至200毫克/公升之間，但是可為50毫克/公升至500毫克/公升之範圍。丁炔二醇之較佳範圍為60至120毫克/公升，但是可為30至300毫克/公升之範圍。較佳為將己炔二醇與丁炔二醇一起使用。如果將其單獨使用則可使用甚至更高濃度之此等化合物。如果使用兩種二醇，則總濃度可為50毫克/公升至600毫克/公升之範圍。The concentration of hexynediol should be between 100 and 200 mg/liter, but can range from 50 mg/liter to 500 mg/liter. The preferred range of butynediol is from 60 to 120 mg/liter, but may range from 30 to 300 mg/liter. Preferably, hexynediol is used together with butynediol. Even higher concentrations of these compounds can be used if used alone. If two diols are used, the total concentration can range from 50 mg/liter to 600 mg/liter.
本發明之一個重要態樣為鎳電鍍浴中不需要醛而提供可接受之STEP結果。“STEP”為「同步厚度及電解電位」之字首，且以稱為STEP測試機之特殊裝置測量，其不僅測量特定沉積物之厚度，亦及光亮與半光亮鎳層間之電位差。此差非常重要，因為其有關這對鎳層之腐蝕保護。STEP須為至少100毫伏且希望為120毫伏或更高。其通常添加醛而完成此點。然而因為此等化合物增加內部應力且亦降低半光亮塗層之延展性與調平，所以不希望使用醛。An important aspect of the invention is that the acetal is not required in the nickel plating bath to provide acceptable STEP results. "STEP" is the prefix of "synchronous thickness and electrolytic potential" and is measured by a special device called the STEP tester, which measures not only the thickness of a particular deposit, but also the potential difference between the bright and semi-bright nickel layers. This difference is very important because of its corrosion protection against the nickel layer. The STEP must be at least 100 millivolts and desirably 120 millivolts or higher. It usually does this by adding an aldehyde. However, since these compounds increase internal stress and also reduce the ductility and leveling of the semi-bright coating, it is undesirable to use an aldehyde.
組合所列酸成分與己炔二醇及丁炔二醇而得之結果相當令人意外。使用具有以上添加劑之電鍍浴製備之沉積物的STEP結果為80至145毫伏之範圍。為了得到更高之STEP結果及較佳之調平，pH應較佳為4.0以上，較佳為高於4.5。此較高pH為吾所欲，因為其亦改良沉積物之調平。所提議浴之pH較佳為4.0至5.0，更佳為4.4至4.8，最佳為4.4至4.6。沉積物之應力仍非常低且延展性非常高之事實令人意外。通常據此提高半光亮鎳浴或任何鎳電鍍浴之pH，則沉積物之內部應力上升且延展性較差。The results obtained by combining the listed acid components with hexynediol and butynediol are quite surprising. The STEP results for deposits prepared using an electroplating bath with the above additives ranged from 80 to 145 millivolts. In order to obtain higher STEP results and better leveling, the pH should preferably be 4.0 or higher, preferably higher than 4.5. This higher pH is desirable because it also improves the leveling of the deposit. The pH of the proposed bath is preferably from 4.0 to 5.0, more preferably from 4.4 to 4.8, most preferably from 4.4 to 4.6. The fact that the stress of the sediment is still very low and the ductility is very high is surprising. Generally, the pH of the semi-bright nickel bath or any nickel plating bath is increased accordingly, and the internal stress of the deposit rises and the ductility is poor.
在此所述之半光亮鎳電鍍浴亦提供一種呈現依照克萊斯勒(Chrysler)延展性方法為0.5之完美延展性，及範圍為約2,000 psi壓縮至約4,000 psi拉伸之低內部應力的鎳沉積物。The semi-bright nickel electroplating bath described herein also provides a nickel deposit exhibiting a perfect ductility of 0.5 according to the Chrysler ductility method and a low internal stress ranging from about 2,000 psi to about 4,000 psi. .
此外由本發明電鍍浴電鍍之沉積物的調平相當於新鮮製成之薰草素/甲醛浴。迄今雖已有許多各種方法之調平特徵的專利，其仍無接近新鮮薰草素浴之調平的無薰草素電鍍法。Furthermore, the leveling of the deposits electroplated by the electroplating bath of the present invention corresponds to a freshly prepared xanthan/formaldehyde bath. Although there have been many patents for the leveling characteristics of various methods to date, there is still no lavender-free plating method that is close to the level of fresh lavender bath.
本發明之電鍍浴達成之STEP結果為完全意料外。添加其他之酸(如柳酸與苯甲酸)已實際上證明降低STEP。另外，增加浴之pH以增加STEP亦為完全意料外。The STEP results achieved by the electroplating bath of the present invention were completely unexpected. The addition of other acids (such as salicylic acid and benzoic acid) has actually proven to reduce STEP. In addition, increasing the pH of the bath to increase STEP is also completely unexpected.
沉積物之應力係使用各種方法測量，且一般希望為15,000 psi或更小之範圍內。內部應力越小則越佳。The stress of the deposit is measured using a variety of methods and is generally desired to be in the range of 15,000 psi or less. The smaller the internal stress, the better.
延展性係使用克萊斯勒延展性方法測量。克萊斯勒延展性方法涉及電鍍0.001吋厚之箔。然後將箔切成測微器夾片寬之裁片，且在測微器之夾片中折疊成“U”形。將測微器下壓直到箔破裂且延展性等於T/2R，其中T為電鍍箔之厚度，及2R為箔本身彎曲而破裂之偏差測量。例如如果鎳厚度為0.001”及箔在直徑0.005破裂，則延展性為：D=0.001/0.005=0.2。完美延展性為0.5，且大部分汽車公司要求至少0.4之值。The ductility is measured using the Chrysler ductility method. The Chrysler ductility method involves plating 0.001 inch thick foil. The foil is then cut into pieces of the micrometer clip width and folded into a "U" shape in the clip of the micrometer. The micrometer is pressed down until the foil breaks and the ductility is equal to T/2R, where T is the thickness of the plated foil and 2R is the deviation measurement of the crack of the foil itself. For example, if the nickel thickness is 0.001" and the foil breaks at a diameter of 0.005, the ductility is: D = 0.001 / 0.005 = 0.2. The perfect ductility is 0.5, and most automotive companies require a value of at least 0.4.
本發明現在參考以下之非限制實施例而討論。The invention will now be discussed with reference to the following non-limiting examples.
製備具有40盎司/加侖之硫酸鎳六水合物、4.5盎司/加侖之氯化鎳六水合物與5.5盎司/加侖之硼酸的原料半光亮鎳浴。將溶液經碳與過氧化物處理且過濾，及將pH調整成3.8至4.0。然後添加0.3% v/v之6重量%二己基硫琥珀酸鈉溶液。A semi-bright nickel bath of 40 oz/gal nickel sulfate hexahydrate, 4.5 ounces per gallon of nickel chloride hexahydrate and 5.5 ounces per gallon of boric acid was prepared. The solution was treated with carbon and peroxide and filtered, and the pH was adjusted to 3.8 to 4.0. A 0.3% v/v 6% by weight solution of sodium dihexyl succinate was then added.
將330立方米之此溶液加入裝有氣動攪拌槽之赫耳(hull)電池且加熱至135℉。將2克/公升之乙酸鈉加入浴且將黃銅板以2安培電鍍15分鐘。獲得之沉積物為完全灰暗及具有光澤之凹處。添加0.1%之70/30己炔二醇與丁炔二醇混合物使得總濃度為0.15克/公升。獲得之沉積物在約0至40 ASF為有光澤至半光亮，及在高於40 ASF無光澤，且在接近高電流密度(HCD)邊緣為非常無光澤。330 cubic meters of this solution was added to a hull battery equipped with a pneumatic stirring tank and heated to 135 °F. 2 g/L of sodium acetate was added to the bath and the brass plate was plated at 2 amps for 15 minutes. The deposit obtained was a completely dark and shiny recess. A 0.1% mixture of 70/30 hexynediol and butynediol was added to give a total concentration of 0.15 g/liter. The resulting deposits are glossy to semi-bright at about 0 to 40 ASF, and dull at above 40 ASF, and very dull at the edge near high current density (HCD).
添加另一0.1%之己炔二醇與丁炔二醇混合物，且將板使用有刮痕赫耳電池板重複以測試。有刮痕赫耳電池板為板之底部0.75吋已以200粒砂帶拋光者。其留下拋光線且可使研究者評估橫跨大電流密度範圍之調平。Another 0.1% mixture of hexynediol and butynediol was added and the panels were tested using a scratched Hercules panel for testing. There are scratched Hertz panels for the bottom of the board 0.75 吋 has been polished with 200 abrasive belts. It leaves a polishing line and allows the investigator to evaluate the leveling across a range of large current densities.
全部沉積物在約0至50 ASF均為過度光澤半光亮，及在高於50 ASF無光澤且沿HCD邊緣為非常無光澤。All deposits were overly lustrous semi-bright at about 0 to 50 ASF, and dull at above 50 ASF and very dull along the edge of the HCD.
然後將此板在光亮鎳浴中直接橫跨陽極(非赫耳電池)以25 ASF電鍍5分鐘。此等條件下之光亮鎳不提供太多之調平，而是使沉積物光亮到足以評估起初鎳沉積物之調平。沉積物之調平為薰草素浴之約65%。應注意，板之HCD區域仍混濁，因為半光亮沉積物無光澤。The plate was then plated directly across the anode (non-Her battery) in a bright nickel bath at 25 ASF for 5 minutes. The bright nickel under these conditions does not provide much leveling, but rather brightens the deposit enough to assess the initial leveling of the nickel deposit. The leveling of the sediment is about 65% of the bath of the oxacillin. It should be noted that the HCD area of the panel is still cloudy because the semi-bright deposits are dull.
將新鮮之半光亮原料溶液加入空氣攪拌赫耳電池。然後將2.0克/公升之單氯乙酸鈉加入浴且添加0.2%之己炔二醇與丁炔二醇混合物，使得總濃度為0.30克/公升。將有刮痕黃銅板以2安培電鍍15分鐘。獲得之沉積物為完全有光澤半光亮，但在板之極端HCD邊緣有一些輕微灰暗。如實施例1所述，將板以光亮鎳過度電鍍5分鐘，及調平為全薰草素浴之約65%。Add the fresh, semi-bright stock solution to the air agitated Herr cell. 2.0 g/L of sodium monochloroacetate was then added to the bath and a mixture of 0.2% hexynediol and butynediol was added to give a total concentration of 0.30 g/liter. The scratched brass plate was plated at 2 amps for 15 minutes. The deposit obtained was completely shiny and semi-bright, but there was some slight darkness at the edge of the extreme HCD of the board. The panels were overplated with bright nickel for 5 minutes as described in Example 1 and leveled to approximately 65% of the full Kaempfer bath.
重複實施例2，但是將浴pH增至4.6。獲得之沉積物稍微較實施例2光亮。如上將其以光亮鎳過度電鍍5分鐘且評估調平。沉積物之調平幾乎等於由全薰草素浴電鍍者。增加己炔二醇與丁炔二醇混合物之濃度使得總濃度為0.45克/公升。現在沉積物之調平等於由全薰草素浴電鍍者。Example 2 was repeated but the bath pH was increased to 4.6. The obtained deposit was slightly brighter than in Example 2. It was overplated with bright nickel for 5 minutes as above and evaluated for leveling. The leveling of the sediment is almost equal to that of the whole lavender bath. The concentration of the mixture of hexynediol and butynediol was increased so that the total concentration was 0.45 g/liter. The sediments are now equal to those electroplated by the full lavender bath.
使用4克/公升之單氯乙酸鈉重複實施例2與3之測試，且結果相同。The tests of Examples 2 and 3 were repeated using 4 g/L of sodium monochloroacetate and the results were the same.
以4.6之浴pH重複實施例1。雖然浴呈現改良之調平，但沉積物太無光澤而無實用價值。Example 1 was repeated at a bath pH of 4.6. Although the bath exhibited an improved leveling, the deposit was too dull and of no practical value.
將實例3之浴的1公升溶液置於裝有空氣攪拌槽之燒杯中。由此浴電鍍之箔具有約1.0 mil之厚度。其係在不銹鋼板上以40 ASF之平均電流密度電鍍沉積物而完成。因為基板為鈍性，所以沉積物易藉由切割板之邊緣而移除，其釋放沉積物。如此使鐵板工切割箔裁片及測量延展性。此沉積物之延展性(T/2R)為0.5。One liter of the bath of Example 3 was placed in a beaker containing an air agitation tank. The bath plated foil thus has a thickness of about 1.0 mil. This was done by plating the deposit on a stainless steel plate at an average current density of 40 ASF. Because the substrate is blunt, the deposit is easily removed by the edges of the cutting plate, which releases deposits. This allows the iron sheeter to cut the foil pieces and measure the ductility. The deposit has a ductility (T/2R) of 0.5.
將實例3之浴的1公升溶液再度置於空氣攪拌燒杯中。此回使用裁片法測量應力。其係藉由測量裁片在電鍍前後之偏差，及將資料代入公式[其使用沉積物厚度、偏差、及常數測定單位為每平方吋磅數(psi)之應力]而完成。沉積物之應力經測定為1560 psi拉伸。如上所述，應力越低則越佳，且大部分半光亮鎳沉積物具有約8,000至約15,000 psi拉伸之應力值。One liter of the bath of Example 3 was again placed in an air stirred beaker. This time, the stress is measured using the piece method. This is done by measuring the deviation of the piece before and after electroplating, and substituting the data into a formula [which uses sediment thickness, deviation, and constant measurement in pounds per square inch (psi)). The stress of the deposit was determined to be 1560 psi tensile. As noted above, the lower the stress, the better, and most of the semi-bright nickel deposits have a tensile stress value of from about 8,000 to about 15,000 psi.
使用2克/公升之甲酸鈉代替乙酸鈉而重複實施例1。以二醇獲得之沉積物在全部電流密度範圍均為完全有光澤，但是沉積物具有尚可至不良之調平。雖然增加pH則改良調平，但調平仍小於全薰草素浴之50%。Example 1 was repeated using 2 g/L of sodium formate instead of sodium acetate. The deposits obtained with the diol are completely glossy over the entire range of current densities, but the deposits have a poor to normal leveling. Although the pH is improved and the leveling is improved, the leveling is still less than 50% of the total lavender bath.
評估得自以上實施例之板及其他類似測試板(其經半光亮與光亮鎳電鍍)的STEP。通常結果顯示在較低pH值(例如3.8至4.0)電鍍之沉積物具有約50至80毫伏之STEP值。在pH 4.4至4.6電鍍之沉積物具有110至145毫伏之值。STEP from the plates of the above examples and other similar test plates, which were semi-bright and bright nickel plated, were evaluated. Typical results show that the deposited deposit at a lower pH (e.g., 3.8 to 4.0) has a STEP value of about 50 to 80 millivolts. Deposits plated at pH 4.4 to 4.6 have a value of 110 to 145 millivolts.
如此可知，在此所述之半光亮鎳電鍍浴在非常廣泛之電流密度範圍製造無硫半光亮沉積物。其為已知產生等於全薰草素浴之調平的唯一非薰草素半光亮浴。該浴不需要醛而達成STEP，結果沉積物具有極低之應力及優良之延展性。Thus, the semi-bright nickel electroplating bath described herein produces sulfur-free semi-bright deposits over a very wide range of current densities. It is the only non-inhalant semi-bright bath known to produce a leveling equal to the full periwinin bath. The bath does not require aldehydes to achieve STEP, resulting in deposits with very low stress and excellent ductility.
Claims (29)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/620,746 US20110114498A1 (en) | 2009-11-18 | 2009-11-18 | Semi-Bright Nickel Plating Bath and Method of Using Same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201122162A TW201122162A (en) | 2011-07-01 |
| TWI421382B true TWI421382B (en) | 2014-01-01 |
Family
ID=44010494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW099135543A TWI421382B (en) | 2009-11-18 | 2010-10-19 | Semi-bright nickel plating bath and method of using same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20110114498A1 (en) |
| TW (1) | TWI421382B (en) |
| WO (1) | WO2011062693A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110155582A1 (en) | 2009-11-18 | 2011-06-30 | Tremmel Robert A | Semi-Bright Nickel Plating Bath and Method of Using Same |
| US11685999B2 (en) | 2014-06-02 | 2023-06-27 | Macdermid Acumen, Inc. | Aqueous electroless nickel plating bath and method of using the same |
| JP2020524746A (en) * | 2017-06-23 | 2020-08-20 | アトテック ドイチェランド ゲーエムベーハー | Nickel electroplating bath for depositing a decorative nickel coating on a substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953304A (en) * | 1975-06-23 | 1976-04-27 | Dart Industries Inc. | Electroplating baths for nickel and brightener-leveler compositions therefor |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2841602A (en) * | 1955-10-04 | 1958-07-01 | Udylite Res Corp | Alkynoxy acids |
| GB1114615A (en) * | 1965-03-26 | 1968-05-22 | Harshaw Chem Corp | Electrodeposition of nickel |
| GB1166631A (en) * | 1965-12-07 | 1969-10-08 | Vickers Ltd Sa | Improvements in or relating to the Electrodeposition of Base Metals |
| GB1192036A (en) * | 1966-10-18 | 1970-05-13 | M & T Chemicals Inc | Improvements in or relating to Nickel Electroplating |
| US3745097A (en) * | 1969-05-26 | 1973-07-10 | M & T Chemicals Inc | Electrodeposition of an iridescent chromium coating |
| GB1386781A (en) * | 1971-03-05 | 1975-03-12 | Albright & Wilson | Electrodeposition of nickel |
| US3677913A (en) * | 1971-04-01 | 1972-07-18 | M & T Chemicals Inc | Nickel plating |
| DE2210879C3 (en) * | 1972-03-07 | 1978-06-15 | Hoechst Ag, 6000 Frankfurt | Process for the single bath dyeing of unmodified polyolefin fibers with metal-containing phthalocyanine dyes |
| US4049509A (en) * | 1972-05-16 | 1977-09-20 | W. Canning & Company Limited | Plating |
| GB1541118A (en) * | 1976-12-03 | 1979-02-21 | Bnf Metals Tech Centre | Nickel plating |
| US4310389A (en) * | 1980-06-16 | 1982-01-12 | Chrysler Corporation | Method for simultaneous determination of thickness and electrochemical potential in multilayer plated deposits |
| US4441969A (en) * | 1982-03-29 | 1984-04-10 | Omi International Corporation | Coumarin process and nickel electroplating bath |
| US4554219A (en) * | 1984-05-30 | 1985-11-19 | Burlington Industries, Inc. | Synergistic brightener combination for amorphous nickel phosphorus electroplatings |
| US5338342A (en) * | 1993-05-21 | 1994-08-16 | Mallory Jr Glen O | Stabilized electroless nickel plating baths |
| US5413874A (en) * | 1994-06-02 | 1995-05-09 | Baldwin Hardware Corporation | Article having a decorative and protective multilayer coating simulating brass |
| AU783229B2 (en) * | 1999-08-31 | 2005-10-06 | Remedy Research Limited | Metal-containing compositions, preparations and uses |
| CA2362244A1 (en) * | 2001-11-14 | 2003-05-14 | Peter Forth | Method of treating an electroplating bath |
| WO2004072320A2 (en) * | 2003-02-07 | 2004-08-26 | Pavco, Inc. | Use of n-allyl substituted amines and their salts as brightening agents in nickel plating baths |
| US20110155582A1 (en) * | 2009-11-18 | 2011-06-30 | Tremmel Robert A | Semi-Bright Nickel Plating Bath and Method of Using Same |
-
2009
- 2009-11-18 US US12/620,746 patent/US20110114498A1/en not_active Abandoned
-
2010
- 2010-10-06 WO PCT/US2010/051636 patent/WO2011062693A1/en active Application Filing
- 2010-10-19 TW TW099135543A patent/TWI421382B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3953304A (en) * | 1975-06-23 | 1976-04-27 | Dart Industries Inc. | Electroplating baths for nickel and brightener-leveler compositions therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201122162A (en) | 2011-07-01 |
| WO2011062693A1 (en) | 2011-05-26 |
| US20110114498A1 (en) | 2011-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5796083B2 (en) | Dark chrome electrodeposits | |
| US9790607B1 (en) | 3-(carbamoyl) pyridinium-1-YL-propane-1-sulfonates useful in electroplating baths | |
| EP2683853B1 (en) | Semi-bright nickel plating bath and method of using same | |
| TWI421382B (en) | Semi-bright nickel plating bath and method of using same | |
| CN102953094B (en) | Semi-bright nickel electroplating solution additive, semi-bright nickel electroplating solution and semi-bright nickel electroplating method | |
| TWI670398B (en) | Nickel electroplating compositions with cationic polymers and methods of electroplating nickel | |
| US2026718A (en) | Electrodeposition of metals | |
| NO147994B (en) | PROCEDURE FOR THE PREPARATION OF AN ELECTROLYTIC DEPOSIT AND PLATING SOLUTION FOR EXECUTING THE PROCEDURE | |
| US3715289A (en) | Brightener composition for acid copper electroplating baths | |
| TW201905243A (en) | Nickel plating bath for depositing decorative nickel coating on a substrate | |
| KR20100121399A (en) | Nickel flash plating solution, zinc-electroplated steel sheet and manufacturing method thereof | |
| US2437612A (en) | Process for electrolytically zinc plating magnesium and magnesium base alloys | |
| US3528895A (en) | Plating low stress bright rhodium | |
| Fink et al. | The Deposition of Nickel‐Cobalt Alloys | |
| KR20200012351A (en) | Zn-Ni ALLOY PLATING SOLUTION FOR AUTOMOTIVE PARTS | |
| US11408085B2 (en) | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or semi-bright nickel alloy coating | |
| JP6660421B2 (en) | Nickel electroplating composition containing copolymer of arginine and bisepoxide and method for electroplating nickel | |
| Watts | The plating on radiator shells | |
| CN105132971A (en) | Cr-Ni-Fe alloy electroplating solution and electroplating method | |
| GB2079788A (en) | Process for the electrodeposition of nickel having a high degree of brightness and smoothness | |
| Manquen | Nickel Plated Finishes for Glare Reduction | |
| Pearson | The Control of Chromium Plating Solutions | |
| Macnaughtan et al. | Part II.—The Effect of Deformation on the Protective Value of Hot-Dipped and Electrodeposited Tin Coatings on Steel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |