このような金属と非金属を分割する境界線の概念は、少なくとも1869年より古い文献において記述されている。1891年、ウォーカーは金属と非金属の境界として周期表上に斜めの直線を引いて「図表化」したものを公表した。1906年、アレクサンダー・スミス(英語版)は、彼の非常に影響力のある教科書Introduction to General Inorganic Chemistryにおいて、非金属を残りの元素から分離するジグザグの線を周期表上に含めた。
1923年、アメリカの化学者であるホーレス・グローブス・デミングは、彼の書いた教科書General Chemistry: An elementary surveyにおいて、金属と非金属を分離する階段状の線を短周期表(メンデレーエフの周期表)および各族を18列に並べた通常の周期表のそれぞれに含めた。1928年、メルクは当時アメリカの学校で広く流布していたデミングの18列の周期表を配布する準備を行い、1930年代までにはデミングの周期表は化学のハンドブックや百科事典にまで掲載されるようになった。それはまた、サージェント・ウェルチ(英語版)社によって長年配布され続けた。
1811年もしくは1812年、イェンス・ベルセリウスは、非金属元素がオキソアニオンを形成する能力(例えばクロムがクロム酸イオンCrO42-を形成するように多くの金属がオキソアニオンを形成するのと同様に、例えば硫黄が硫酸イオンSO42-を形成するように非金属元素もオキソアニオンを形成する)に関して半金属と呼称した。ベルセリウスの用いた半金属という語の用法は広く採用されたが、それはその後の論評者らによって直観に反する、誤用される、妥当でない、もしくは説得力がないと評価された。1825年、ベルセリウスのTextbook of Chemistryの改定されたドイツ語版において、ベルセリウスは自らが定義した半金属の概念を3種類に再分割した。1つは常に気体である「gazloyta」(水素、窒素、酸素)、1つは真の半金属「metalloid」(硫黄、リン、炭素、ホウ素、ケイ素)、そしてもう1つは塩を形成する「halogenia」(フッ素、塩素、臭素、ヨウ素)である。1845年に発行されたA dictionary of science, literature and artにおいて、ベルセリウスによる元素の分類は「I. gazolytes; II. halogens; III. metalloids(一定の側面においては金属に類似しているが、他は広く異なっている); IV. metals」と表された。
1920年代間、半金属という用語の2つの意味は流行の移り変わりを受けているように見えた。コーチはA Dictionary of Chemical Termsにおいて、「半金属」とは「非金属」の古くすたれた言い方であると定義した。一方でWebster 's New International Dictionaryにおいては、非金属を言及するための半金属という用語の使用は、ヒ素やアンチモン、テルルのような典型的な金属に類似した元素へ何らかの方法で適用される基準として注記された。半金属という用語の使用は、その後1940年までの間大きく流動していた。半金属の用語を中間もしくは境界線上の元素に対して適用するという合意は、続く1940年から1960年の間には起こらなかった。
1947年、ライナス・ポーリングは、彼の古典的かつ影響力のあるテキストであるGeneral chemistry: An introduction to descriptive chemistry and modern chemical theoryにおいて、半金属についての言及を行った。ポーリングは半金属を中間的な性質を有する元素である…ホウ素、ケイ素、ゲルマニウム、ヒ素、アンチモン、テルル、ポロニウムを含み、[周期表上で]斜めの領域を占領していると記述した。1959年、国際純正・応用化学連合 (IUPAC)は、たとえ半金属という用語が非金属の概念を意味する用語としてフランス人などの間でいまだ使われているとしても、半金属という用語は非金属を表すために用いてはならないと勧告した。
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